Catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer

ABSTRACT

An electron-withdrawing group-containing metal compound (I) of an atom of the Group III to the Group XII or lanthanide series of the Periodic Table of the Elements, a catalyst component for addition polymerization composed of the compound (I), a catalyst for addition polymerization obtained by contacting the compound (I) with a specific compound (II) of metal of the Group III to the Group XIII or lanthanide series and optionally an organoaluminum compound (III), and a process for producing an addition polymer using the catalyst.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a catalyst component for additionpolymerization, a catalyst for addition polymerization made by usingthereof, and a process for producing an addition polymer.

2. Description of Related Arts

Since olefin polymers such as polypropylene and polyethylene areexcellent in mechanical properties, chemical resistance and the like andexcellent in balance between those properties and economical efficiency,they have been widely used for various molding fields. These olefinpolymers have been conventionally produced by polymerizing an olefinusing a conventional type solid catalyst (multi-site catalyst) whichcombines a solid catalyst component obtained by using a metal compoundof Group IV such as titanium trichloride or titanium tetrachloride, witha metal compound of Group XIII represented by an organoaluminumcompound.

A process for producing an addition polymer, which polymerizes anaddition-polymerizable monomer using a so-called single site catalystprepared by combining a transition metal compound which is differentfrom a solid catalyst component having been used from old (for example,a metallocene complex) with an aluminoxane or the like, is recentlyproposed. For example, JP-A-58-19309 reports a process usingbis(cyclopentadienyl) zirconium dichloride and methyl aluminoxane.Further, it is reported that a specific boron compound and suchtransition metal compound are combined. For example, JP-A-1-50203reports a process using bis(cyclopentadienyl)zirconium dimethyl andtri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate. The olefinpolymers obtained by using these single site catalysts have a narrowermolecular weight distribution than that obtained by the conventionaltype solid catalyst (multi-site catalyst), and further, a comonomer ismore homogeneously copolymerized in case of a copolymer. Accordingly, itis known that a more homogeneous copolymer than a case of using theconventional type solid catalyst is obtained.

The improvement of such catalyst component for addition polymerizationhas been intensively studied, and the kinds of metals used for maincatalyst components are widely reported over the respective Groups ofthe Periodic Table. For example, in Angew. Chem. Int. Ed. 38 428 (1999),it reported that a metallocene complex of the Group III to the GroupXIII and non-metallocene compound are effective as the main catalystcomponents. On the other hand, as a co-catalyst component as anactivator for combining with the metallocene complex or non-metallocenecompound, an aluminoxane belonging to a compound of the Group XIII, aboron compound and the like have been mainly developed.

Further, when an addition polymer such as an olefin polymer is producedusing a single-site catalyst, the molecular weight of the additionpolymer obtained is usually low, and the improvement thereof has beendesired. JP-A-6-329713 reports a catalyst component of polymerizing anolefin composed of an aluminum compound having an electron withdrawinggroup or a group containing an electron withdrawing group. An olefinpolymer having a certain degree of high molecular weight can be obtainedby using the aluminum compound. However, since it cannot be always saidthat the high molecular weight is adequately high, a novel catalystcomponent as an activator, which realizes the further improvement ofhigh molecular weight, has been desired.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a compound capable offorming a catalyst for addition polymerization which reveals a highpolymerization activity by using as a catalyst aid component foractivation and a production method thereof, a catalyst component foraddition polymerization composed of a compound, capable of forming acatalyst for addition polymerization which reveals a high polymerizationactivity, a catalyst for addition polymerization which is made by usingthe catalyst component and reveals a high polymerization activity, andan efficient process for producing an addition polymer using thecatalyst for addition polymerization.

Namely, according to the present invention, an electron withdrawinggroup-containing metal compound (I) selected from the group consistingof [A] to [E] described below, a catalyst component for additionpolymerization composed of the compound(I), a catalyst for additionpolymerization prepared by contacting a transition metal complex (II)therewith or by contacting a transition metal complex (II) and anorganoaluminum compound(III) therewith, and a process for producing anaddition polymer with the catalyst for addition polymerization areprovided:

[A] A compound obtained by contacting (a), (b) and (c) described belowin the presence of an ether compound as a solvent:

(a) a compound represented by the general formula [1],

M¹L¹c  [1]

(b) a compound represented by the general formula [2],

R¹ _(p-1)T¹H  [2], and

(c) a compound represented by the general formula [3],

R² _(q-2)J¹H₂  [3]

(wherein in each of the general formulae [1] to [3], M¹ represents anatom of the Group III to the Group XII or lanthanide series of thePeriodic Table; c represents a valence of M¹; L¹ represents a hydrogenatom, a halogen atom or a hydrocarbon group; when a plural number ofL¹'s exist, they may be mutually the same or different; R¹ represents anelectron-withdrawing group or a group containing an electron-withdrawinggroup; R² represents a hydrocarbon group or a halogenated hydrocarbongroup; when a plural number of R²'s exist, they may be mutually the sameor different; each of T¹ and J¹ independently represents an atom ofGroup XV or Group XVI of the Periodic Table; and each of p and qrepresents a valence of T¹ and J¹, respectively.);

[B] A compound obtained by contacting (d), (e) and (f) described below:

(d) a compound represented by the general formula [4],

M²L²d  [4]

(e) a compound represented by the general formula [5],

R³ _(r-1)T²H  [5], and

(f) a compound represented by the general formula [6];

R⁴(J²H_(e-1))_(f)  [6]

(wherein in each of the general formulae [4] to [6], M² represents anatom of Group III to Group XII or lanthanide series of the PeriodicTable; d represents a valence of M²; L² represents a hydrogen atom, ahalogen atom or a hydrocarbon group; when a plural number of L²'s exist,they may be mutually the same or different; R³ represents anelectron-withdrawing group or a group containing an electron-withdrawinggroup; R⁴ represents an organic group having a valence of f; each of T²and J² independently represents an atom of the Group XV or Group XVI ofthe Periodic Table; r represents a valence of T²; e represents a valenceof J²; and “f” is an integer of 2 to 10.);

[C] A compound represented by the general formula [7]:

(wherein M³ represents an atom of the Group III to Group XII orlanthanide series of the Periodic Table; when a plural number of M³'sexist, they may be mutually the same or different; T³ represents an atomof the Group XIV, Group XV or Group XVI of the Periodic Table; when aplural number of T³'s exist, they may be mutually the same or different;R⁵ represents an electron-withdrawing group or a group containing anelectron-withdrawing group; when a plural number of R⁵'s exist, they maybe mutually the same or different; R⁶ represents a hydrocarbon group; aplural number of R⁶'s may be mutually the same or different; “g”represents a valence of M³; “s” represents a valence of T³; and “h”represents a numeral of 1 or more.);

[D] A compound represented by the general formula [8],

M⁴(X¹R⁷ _(i))_(t)R⁸ _(j-t)  [8]

(wherein M⁴ represents an atom of the Group III to Group XII orlanthanide series of the Periodic Table; X¹ represents an atom of theGroup XIV, Group XV or Group XVI of the Periodic Table; when a pluralnumber of X¹'s exist, they may be mutually the same or different; R⁷represents an electron-withdrawing group or a group containing anelectron-withdrawing group; when a plural number of R⁷'s exist, they maybe mutually the same or different; R⁸ represents a hydrogen atom, ahalogen atom or a hydrocarbon group; a plural number of R⁸'s may bemutually the same or different; “j” represents a valence of M⁴; “t”represents a numeral satisfying 0<t≦j; and “i” represents a numeral lessby one than the valence of X¹); and

[E] A compound represented by the general formula [9]:

[(R⁹ _(u-1)X²)k⁻¹ M⁵O]_(m) T⁴R¹⁰ _(3-m)  [9]

(wherein M⁵ represents an atom of the Group III to Group XII orlanthanide series of the Periodic Table; when a plural number of M⁵'sexist, they may be mutually the same or different; X² represents an atomof the Group XIV, Group XV or Group XVI of the Periodic Table; when aplural number of X²'s exist, they may be mutually the same or different;R⁹ represents an electron-withdrawing group or a group containing anelectron-withdrawing group; when a plural number of R⁹'s exist, they maybe mutually the same or different; T⁴ represents an atom of the GroupXIII of the Periodic Table, R¹⁰ represents a hydrogen atom, a halogenatom or a hydrocarbon group; when a plural number of R¹⁰'s exist, theymay be mutually the same or different; “k” represents a valence of M⁵;“u” represents a valence of X²; and “m” represents a numeral satisfying1≦m≦3.)

Further, the present invention is illustrated in detail below.

DETAILED DESCRIPTION OF THE INVENTION

Respective M¹ to M⁵ in the general formulae [1], [4], [7], [8] and [9]represent an atom of the Group III to the Group XII or lanthanide seriesof the Periodic Table of the Elements (Revised edition of IUPACInorganic Chemistry Nomenclature 1989). Specific examples thereofinclude a scandium atom, an yttrium atom, a titanium atom, a zirconiumatom, a vanadium atom, a chromium atom, a molybdenum atom, a manganeseatom, a rhenium atom, an iron atom, a ruthenium atom, a cobalt atom, arhodium atom, a nickel atom, a palladium atom, a platinum atom, a copperatom, a silver atom, a gold atom, a zinc atom, a cadmium atom, a mercuryatom, a samarium atom, an ytterbium atom and the like. As M¹ to M⁵, anatom of the Group XII is preferable in particular, and a zinc atom ismost preferable.

Respective c, d, g, j and k in the general formulae [1], [4], [7], [8]and [9] represent a valence of Ml to M⁵, respectively, and for example,when M¹ is a zinc atom, c is 2.

Respective L¹ and L² in the general formulae [1] and [4] represent ahydrogen atom, a halogen atom or a hydrocarbon group, and when a pluralnumber of L¹'s and L²'s exist, they may be mutually the same ordifferent. Specific examples of the halogen atom in L¹ and L² include afluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As ahydrocarbon group in Ll and L2, an alkyl group, an aryl group or anaralkyl group is preferable.

As the alkyl group, an alkyl group having 1 to 20 carbon atoms ispreferable. Examples include thereof a methyl group, an ethyl group, an-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group,a tert-butyl group, an isobutyl group, a n-pentyl group, a neopentylgroup, a n-hexyl group, a n-octyl group, a n-decyl group, a n-dodecylgroup, a n-pentadecyl group, a n-eicosyl group, and the like. A methylgroup, an ethyl group, an isopropyl group, a tert-butyl group or anisobutyl group is more preferable.

Any one of these alkyl groups may be substituted with a halogen atomsuch as a fluorine atom, a chlorine atom, a bromine atom, or an iodineatom. Examples of the alkyl group having 1 to 20 carbon atoms which issubstituted with the halogen atom include a fluoromethyl group, adifluoromethyl group, a trifluoromethyl group, a chloromethyl group, adichloromethyl group, a trichloromethyl group, a bromomethyl group, adibromomethyl group, a tribromomethyl group, an iodomethyl group, adiiodomethyl group, a triiodomethyl group, a fluoroethyl group, adifluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, apentafluoroethyl group, a chloroethyl group, a dichloroethyl group, atrichloroethyl group, a tetrachloroethyl group, a pentachloroethylgroup, a bromoethyl group, a dibromoethyl group, a tribromoethyl group,a tetrabromoethyl group, a pentabromoethyl group, a perfluoropropylgroup, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexylgroup, a perfluorooctyl group, a perfluorododecyl group, aperfluoropentadecyl group, a perfluoroeicosyl group, a perchloropropylgroup, a perchlorobutyl group, a perchloropentyl group, a perchlorohexylgroup, a perchlorooctyl group, a perchlorododecyl group, aperchloropentadecyl group, a perchloroeicosyl group, a perbromopropylgroup, a perbromobutyl group, a perbromopentyl group, a perbromohexylgroup, a perbromooctyl group, a perbromododecyl group, aperbromopentadecyl group, a perbromoeicosyl group and the like.

Further, these alkyl groups may be partially substituted with an alkoxygroup such as a methoxy group, an ethoxy group or the like, an aryloxygroup such as a phenoxy group or the like, or an aralkyloxy group suchas a benzyloxy group or the like, etc.

As the aryl group, an aryl group having 6 to 20 carbon atoms ispreferable. Examples thereof include a phenyl group, a 2-tolyl group, a3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylylgroup, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a3,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a2,3,4,6-tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, apentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group,an isopropylphenyl group, a n-butylphenyl group, a sec-butylphenylgroup, a tert-butylphenyl group, a n-pentylphenyl group, aneopentylphenyl group, a n-hexylphenyl group, a n-octylphenyl group, an-decylphenyl group, a n-dodecylphenyl group, a n-tetradecylphenylgroup, a naphthyl group, an anthracenyl group and the like, and a phenylgroup is more preferable.

These aryl groups may be partially substituted with a halogen atom suchas a fluorine atom, a chlorine atom, a bromine atom or an iodine atom,an alkoxy group such as a methoxy group, an ethoxy group or the like, anaryloxy group such as a phenoxy group or the like, or an aralkyloxygroup such as a benzyloxy group or the like, etc.

As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms ispreferable. Examples thereof include a benzyl group, a(2-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a(4-methylphenyl)methyl group, a (2,3-dimethylphenyl)methyl group, a(2,4-dimethylphenyl)methyl group, a (2,5-dimethylphenyl)methyl group, a(2,6-dimethylphenyl)methyl group, a (3,4-dimethylphenyl)methyl group,(3,5-dimethylphenyl)methyl group, a (2,3,4-timethylphenyl)methyl group,a (2,3,5-timethylphenyl)methyl group, a (2,3,6-timethylphenyl)methylgroup, a (3,4,5-timethylphenyl)methyl group, a(2,4,6-timethylphenyl)methyl group, a (2,3,4,5-tetramethylphenyl)methylgroup, a (2,3,4,6-tetramethylphenyl)methyl group, a(2,3,5,6-tetramethylphenyl)methyl group, a (pentamethylphenyl)methylgroup, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, a n(isopropylphenyl)methyl group, a (n-butylphenyl)methyl group, a(sec-butylphenyl)methyl group, a (tert-butylphenyl)methyl group, a(n-pentylphenyl)methyl group, a (neopentylphenyl)methyl group, a(n-hexylphenyl)methyl group, a (n-octylphenyl)methyl group, a(n-decylphenyl)methyl group, a (n-dodecylphenyl)methyl group, a(n-tetradecylphenyl)methyl group, a naphthylmethyl group, ananthracenylmethyl group and the like, and a benzyl group is morepreferable.

These aralkyl groups may be partially substituted with a halogen atomsuch as a fluorine atom, a chlorine atom, a bromine atom, an iodine atomor the like, an alkoxy group such as a methoxy group, an ethoxy group orthe like, an aryloxy group such as a phenoxy group or the like, or anaralkyloxy group such as a benzyloxy group or the like, etc.

Each of the above-mentioned L¹ and L² is preferably a hydrogen atom, analkyl group or an aryl group, more preferably a hydrogen atom or analkyl group, and preferably an alkyl group in particular.

Respective T¹, J¹, T² and J² in the above-mentioned general formulae[2], [3], [5] and [6]independently represent an atom of the Group XV orGroup XVI of the Periodic Table of the Elements (Revised edition ofIUPAC Inorganic Chemistry Nomenclature 1989). T¹ in the general formula[2] and J¹ in the general formula [3] may be the same or different.Further, T² in the general formula [5] and J² in the general formula [6]may be the same or different. Specific examples of the atom of the GroupXV include a nitrogen atom, a phosphorous atom, and the like, andspecific examples of the atom of the Group XVI include an oxygen atom, asulfur atom, and the like. Respective T¹, J¹, T² and J² are preferably anitrogen atom, or an oxygen atom, and more preferably an oxygen atom.

Respective p, q, r and e in the above-mentioned general formulae [2],[3], [5] and [6] represent a valence of T¹, J¹, T² and J², respectively,and for example, when T¹ is an atom of the Group XV, p is 3 and when T¹is an atom of the Group XVI, p is 2.

Respective R¹ and R³ in the above-mentioned general formulae [2] and [5]represent an electron-withdrawing group or a group containing anelectron-withdrawing group, and when a plural number of R¹'s or R³'sexist, they may be mutually the same or different. As an index of theelectron-withdrawing property, the substituent constant σ of theHammet's rule and the like are known, and a functional group in whichthe substituent constant σ of the Hammet's rule is positive can bementioned as an electron-withdrawing group.

Specific examples of the electron-withdrawing group include a fluorineatom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, anitro group, a carbonyl group, a sulfone group, a phenyl group and thelike.

The group containing an electron-withdrawing group preferably include ahalogenated alkyl group, halogenated aryl, and a (halogenated alkyl)arylgroup, cyanated aryl group and nitrated aryl group having up to 20carbon atoms, an ester group (an alkoxycarbonyl group,aralkyloxycarbonyl group and aryloxycarbonyl group having up to 20carbon atoms,) and the like.

Specific examples of the halogenated alkyl group include a fluoromethylgroup, a chloromethyl group, a bromomethyl group, an iodomethyl group, adifluoromethyl group, a dichloromethyl group, a dibromomethyl group, adiodomethyl group, a trifluoromethyl group, a trichloromethyl group, atribromomethyl group, a triiodomethyl group, a 2,2,2-trifluoroethylgroup, a 2,2,2-trichloroethyl group, a 2,2,2-tribromoethyl group, a2,2,2-triiodoethyl group, a 2,2,3,3,3-pentafluoropropyl group, a2,2,3,3,3-pentachloropropyl group, a 2,2,3,3,3-pentabromopropyl group, a2,2,3,3,3-pentaiodopropyl group, a2,2,2-trifluoro-1-trifluoromethylethyl group, a2,2,2-trichloro-1-trichloromethylethyl group, a2,2,2-tribromo-1-tribromomethylethyl group, a2,2,2-triiodo-1-triiodomethylethyl group, a1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group, a1,1-bis(trichloromethyl)-2,2,2-trichloroethyl group, a1,1-bis(tribromomethyl)-2,2,2-tribromoethyl group, a1,1-bis(triiodomethyl)-2,2,2-triiodoethyl group, and the like.

Specific examples of the halogenated aryl group include a 2-fluorophenylgroup, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenylgroup, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-bromophenylgroup, a 3-bromophenyl group, a 4-bromophenyl group, a 2-iodophenylgroup, a 3-iodophenyl group, a 4-iodophenyl group, a 2,6-difluorophenylgroup, a 3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group, a2,6-dichlorophenyl group, a 3,5-dichlorophenyl group, a2,6-dibromophenyl group, a 3,5-dibromophenyl group, a 2,6-dibodophenylgroup, a 3,5-dibodophenyl group, a 2,4,6-trifluorophenyl group, a2,4,6-trichlorophenyl group, a 2,4,6-tribromophenyl group, a2,4,6-triiodophenyl group, a pentafluorophenyl group, apentachlorophenyl group, a pentabromophenyl group, a pentaiodophenylgroup, and the like.

Specific examples of the (halogenated alkyl)aryl group include a2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a4-(trifluoromethyl)phenyl group, a 2,6-bis(trifluoromethyl)phenyl group,a 3,5-bis(trifluoromethyl)phenyl group, a2,4,6-tris(trifluoromethyl)phenyl group, and the like.

Specific examples of the cyanated aryl group include a 2-cyanophenylgroup, a 3-cyanophenyl group, a 4-cyanophenyl group and the like.

Specific examples of the nitrated aryl group include a 2-nitrophenylgroup, a 3-nitrophenyl group, a 4-nitrophenyl group and the like.

Specific examples of the ester group include a methoxycarbonyl group, anethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonylgroup, a phenoxycarbonyl group, a trifluoromethoxycarbonyl group, apentafluorophenoxycarbonyl group, and the like.

R¹ and R³ are preferably the halogenated hydrocarbon group, and morepreferably the halogenated alkyl group or halogenated aryl group havingup to 20 carbon atoms. Further preferable is a fluoromethyl group, adifluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethylgroup, a 2,2,3,3,3-pentafluoropropyl group, a2,2,2-trifluoro-1-trifluoromethylethyl group, a1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group, a 4-fluorophenylgroup, a 2,6-difluorophenyl group, a 3,5-difluorophenyl group, a3,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, apentafluorophenyl group, a chloromethyl group, a dichloromethyl group, atrichloromethyl group, a 2,2,2-trichloroethyl group, a2,2,3,3,3-pentachloropropyl group, a2,2,2-trichloro-1-trichloromethylethyl group, a1,1-bis(trichloromethyl)-2,2,2-trichloroethyl group, a 4-chlorophenylgroup, a 2,6-dichlorophenyl group, a 3,5-dichlorophenyl group, a2,4,6-trichlorophenyl group or a pentachlorophenyl group. A fluoroalkylgroup or a fluoroaryl group is preferable in particular, and atrifluoromethyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group, a1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group, a3,4,5-trifluorophenyl group, or a pentafluorophenyl group is mostpreferable.

R² represents in the general formula [3] represents a hydrocarbon groupor a halogenated hydrocarbon group, and when a plural number of R²'sexist, they may be mutually the same or different. The hydrocarbon groupin R² is preferably an alkyl group, aryl group or aralkyl group havingup to 20 carbon atoms, and the same hydrocarbon group as illustrated inthe general formula [1] as L¹ is used. The halogenated hydrocarbon groupin R² includes a halogenated alkyl group, halogenated aryl group, or(halogenated alkyl)aryl group having up to 20 carbon atoms, and thelike, and the same halogenated alkyl group, halogenated aryl group, and(halogenated alkyl)aryl group as mentioned as specific examples of theelectron-withdrawing group in R¹ of the general formula [2] are used.

R² in the general formula [3] is preferably a halogenated hydrocarbongroup, and further preferably a fluorinated hydrocarbon group.

R⁴ in the general formula [6] represents an organic group having avalence off, and is preferably a saturated aliphatic hydrocarbon grouphaving a valence of f or an aromatic hydrocarbon group having a valenceof f.

“f” in the general formula [6] is a valence of R⁴ and an integer of 2 to10, preferably an integer of 2 to 6, more preferably an integer of 2 to4, further more preferably an integer of 2 or 3, and most preferably 2.

Specific examples of the compounds (a) and (d) in the case in which eachof M¹ and M² is a zinc atom, include dialkylzincs such as dimethylzinc,diethylzinc, dipropylzinc, di-n-butylzinc, di-isobutylzinc,di-n-hexylzinc, diallylzinc, bis(cyclopentadienyl) zinc and the like;diarylzincs such as diphenylzinc, dinaphthylzinc,bis(pentafluorophenyl)zinc and the like; alkylzinc halides such asmethylzinc chloride, ethylzinc chloride, propylzinc chloride,n-butylzinc chloride, isobutylzinc chloride, n-hexylzinc chloride,methylzinc bromide, ethylzinc bromide, propylzinc bromide, n-butylzincbromide, isobutylzinc bromide, n-hexylzinc bromide, methylzinc iodide,ethylzinc iodide, propylzinc iodide, n-butylzinc iodide, isobutylzinciodide, n-hexylzinc iodide and the like; zinc halides such as zincfluoride, zinc chloride, zinc bromide and zinc iodide; and the like.

The compounds (a) and (d) are preferably dialkylzincs, furtherpreferably dimethylzinc, diethylzinc, dipropylzinc, di-n-butylzinc,di-isobutylzinc, di-n-hexylzinc, diallylzinc orbis(cyclopentadienyl)zinc, and in particular, dimethylzinc ordiethylzinc is preferable.

Specific examples of the compounds (b) and (e) include amines such asdifluoromethylamine, dichloromethylamine, dibromomethylamine,diiodomethylamine, bis(difluoromethyl)amine, bis(dichloromethyl)amine,bis(dibromomethyl)amine, bis(diiodomethyl)amine,bis(trifluoromethyl)amine, bis(trichloromethyl)amine,bis(tribromomethyl)amine, bis(triiodomethyl)amine, bis(2,2,2-trifluoroethyl) amine, bis(2,2,2-trichloroethyl)amine,bis(2,2,2-tribromoethyl)amine, bis(2,2,2-triiodoethyl)amine,bis(2,2,3,3,3-pentafluoropropyl)amine,bis(2,2,3,3,3-pentachloropropyl)amine,bis(2,2,3,3,3-pentabromopropyl)amine,bis(2,2,3,3,3-pentaiodopropyl)amine,bis(2,2,2-trifluoro-1-trifluoromethylethyl)amine,bis(2,2,2-trichloro-1-trichloromethylethyl)amine,bis(2,2,2-tribromo-1-tribromomethylethyl)amine,bis(2,2,2-triiodo-1-triiodomethylethyl)amine,bis(1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl)amine,bis(1,1-bis(trichloromethyl)-2,2,2-trichloroethyl)amine,bis(1,1-bis(tribromomethyl)-2,2,2-tribromoethyl)amine,bis(1,1-bis(triiodomethyl)-2,2,2-triiodoethyl)amine,bis(2-fluorophenyl)amine, bis(3-fluorophenyl)amine,bis(4-fluorophenyl)amine, bis(2-chlorophenyl)amine,bis(3-chlorophenyl)amine, bis(4-chlorophenyl)amine,bis(2-bromophenyl)amine, bis(3-bromophenyl)amine,bis(4-bromophenyl)amine, bis(2-iodophenyl)amine, bis(3-iodophenyl)amine,bis(4-iodophenyl)amine, bis(2,6-difluorophenyl)amine,bis(3,5-difluorophenyl)amine, bis(2,6-dichlorophenyl)amine,bis(3,5-dichlorophenyl)amine, bis(2,6-dibromophenyl)amine,bis(3,5-dibromophenyl)amine, bis(2,6-diiodophenyl)amine,bis(3,5-diiodophenyl)amine, bis(2,4,6-trifluorophenyl)amine,bis(2,4,6-trichlorophenyl)amine, bis(2,4,6-tribromophenyl)amine,bis(2,4,6-triiodophenyl)amine, bis(pentafluorophenyl)amine, bis(pentachorophenyl)amine, bis(pentabromophenyl)amine,bis(pentaiodophenyl)amine, bis(2-(trifluoromethyl)phenyl)amine,bis(3-(trifluoromethyl)phenyl)amine,bis(4-(trifluoromethyl)phenyl)amine,bis(2,6-di(trifluoromethyl)phenyl)amine,bis(3,5-di(trifluoromethyl)phenyl)amine,bis(2,4,6-tri(trifluoromethyl)phenyl)amine, bis(2-cyanophenyl)amine,bis(3-cyanophenyl)amine, bis(4-cyanophenyl)amine,bis(2-nitrophenyl)amine, bis(3-nitrophenyl)amine,bis(4-nitrophenyl)amine and the like. Further, phosphine compounds inwhich a nitrogen atom is replaced with a phosphorus atom in theabove-mentioned amine compounds, and the like are also exemplified.

When the compounds (b) and (e) are alcohols, specific examples thereofinclude fluoromethanol, chloromethanol, bromomethanol, iodomethanol,difluoromethanol, dichloromethanol, dibromomethanol, diiodomethanol,trifluoromethanol, trichloromethanol, tribromomethanol, triiodomethanol,2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol,2,2,2-triiodoethanol, 2,2,3,3,3-pentafluoropropanol,2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol,2,2,3,3,3-pentaiodopropanol, 2,2,2-trifluoro-1-trifluoromethylethanol,2,2,2-trichloro-1-trichloromethylethanol,2,2,2-tribromo-1-tribromomethylethanol,2,2,2-triiodo-1-triiodomethylethanol,1,1-bis(trifluoromethyl)-2,2,2-trifluoroethanol,1,1-bis(trichloromethyl)-2,2,2-trichloroethanol,1,1-bis(tribromomethyl)-2,2,2-tribromoethanol,1,1-bis(triiodomethyl)-2,2,2-triiodoethanol and the like. Further, thiolcompounds in which an oxygen atom is replaced with a sulfur atom in theabove-mentioned alcohol compounds, and the like are also exemplified.

When the compounds (b) and (e) are phenols, specific examples thereofinclude 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol,3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol,4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol,2,6-difluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol,2,6-dichlorophenol, 3,5-dichlorophenol, 2,6-dibromophenol,3,5-dibromophenol, 2,6-diiodophenol, 3,5-diiodophenol,2,4,6-trifluorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol,2,4,6-triiodophenol, pentafluorophenol, pentachlorophenol,pentabromophenol, pentaiodophenol, 2-(trifluoromethyl)phenol,3-(trifluoromethyl)phenol, 4-(trifluoromethyl)phenol,2,6-bis(trifluoromethyl)phenol, 3,5-bis(trifluoromethyl)phenol,2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol,3-nitrophenol, 4-nitrophenol and the like. Further, thiophenol compoundsin which an oxygen atom is replaced with a sulfur atom in theabove-mentioned phenol compounds, and the like are also exemplified.

When the compounds (b) and (e) are carboxylic acids, specific examplesthereof include 2-fluorobenzoic acid, 3-fluorobenzoic acid,4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoicacid, 2,5-difluorobenzoic acid, 2,6-difluorobenzoic acid,2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid,2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid,2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid,2,3,4,6-tetrafluorobenzoic acid, pentafluorobenzoic acid, fluoroaceticacid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropanoicacid, heptafluorobutanoic acid,1,1-bis(trifluoromethyl)-2,2,2-trifluoroehtanoic acid and the like.

When the compounds (b) and (e) are sulfonic acids, specific examplesthereof include fluoromethanesulfonic acid, difluoromethanesulfonicacid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid,heptafluoropropanesulfonic acid,1,1-bis(trifluoromethyl)-2,2,2-trifluoroehtanesulfonic acid and thelike.

The compounds (b) and (e) are preferably, bis(trifluoromethyl)amine,bis(2,2,2-trifluoromethyl)amine, bis(2,2,3,3,3-pentafluoropropyl)amine,bis(2,2,2-trifluoro-1-trifluoromethylethyl)amine,bis(1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl)amine orbis(pentafluorophenyl)amine as amines; trifluoromethanol,2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol,2,2,2-trifluoro-1-trifluoromethylethanol or1,1-bis(trifluoromethyl)-2,2,2-trifluoroethanol as alcohols;2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol,3,5-difluorophenol, 3,4,5-trifluorophenol, 2,4,6-trifluorophenol,pentafluorophenol, 2-(trifluoromethyl)phenol, 3-(trifluoromethyl)phenol,4-(trifluoromethyl)phenol, 2,6-bis(trifluoromethyl)phenol,3,5-bis(trifluoromethyl)phenol or 2,4,6-tris(trifluoromethyl)phenol asphenols; pentafluorobenzoic acid or trifluoroacetic acid as carboxylicacids; and trifluoromethanesulfonic acid as sulfonic acids.

The compounds (b) and (e) are more preferably,bis(trifluoromethyl)amine, bis(pentafluorophenyl) amine,trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol,1,1-bis(trifluoromethyl)-2,2,2-trifluoroethanol, 4-fluorophenol,2,6-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol,pentafluorophenol, 4-(trifluoromethyl)phenol,2,6-bis(trifluoromethyl)phenol or 2,4,6-tris(trifluoromethyl)phenol, andfurther preferably 3,4,5-trifluorophenol, pentafluorophenol or1,1-bis(trifluoromethyl)-2,2,2-trifluoroethanol.

The compounds (c) are preferably water, hydrogen disulfide, analkylamine, arylamine, aralkylamine halogenated alkylamine, halogenatedarylamine, and (halogenated alkyl)arylamine having up to 20 carbonatoms, and specific examples thereof include water, hydrogen disulfide,methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,sec-butylamine, tert-butylamine, isobutyl amine, n-pentylamine,neopentylamine, amyl amine, n-hexylamine, n-octylamine, n-decyl amine,n-dodecyl amine, n-eicosylamine, allylamine, cyclopentadienylamine,aniline, 2-tolylamine, 3-tolylamine, 4-tolylamine, 2,3-xylylamine,2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine,3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline,2,3,6-trimethylaniline, 2,4,6-trimethylaniline, 3,4,5-trimethylaniline,2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline,2,3,5,6-tetramethylaniline, pentamethylaniline, ethylaniline,n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline,tert-butylaniline, n-pentylaniline, neopentylaniline, n-hexylaniline,n-octylaniline, n-decylaniline, n-dodecylaniline, n-tetradecylaniline,naphthylamine, anthracenylamine, benzylamine,(2-methylphenyl)methylamine, (3-methylphenyl)methylamine,(4-methylphenyl)methylamine, (2,3-dimethylphenyl)methylamine,(2,4-dimethylphenyl)methylamine, (2,5-dimethylphenyl)methylamine,(2,6-dimethylphenyl)methylamine, (3,4-dimethylphenyl)methylamine,(3,5-dimethylphenyl)methylamine, (2,3,4-trimethylphenyl)methylamine,(2,3,5-trimethylphenyl)methylamine, (2,3,6-trimethylphenyl)methylamine,(3,4,5-trimethylphenyl)methylamine, (2,4,6-trimethylphenyl)methylamine,(2,3,4,5-tetramethylphenyl)methylamine,(2,3,4,6-tetramethylphenyl)methylamine,(2,3,5,6-tetramethylphenyl)methylamine, (pentamethylphenyl)methylamine,(ethylphenyl)methylamine, (n-propylphenyl)methylamine,(isopropylphenyl)methylamine, (n-butylphenyl)methylamine,(sec-butylphenyl)methylamine,(tert-butylphenyl)methylamine,(n-pentylphenyl)methylamine,(neopentylphenyl)methylamine, (n-hexylphenyl)methylamine,(n-octylphenyl)methylamine, (n-decylphenyl)methylamine,(n-dodecylphenyl)methylamine, naphtylmethylamine,anthracenylmethylamine, fluoromethylamine, chloromethylamine,bromomethylamine, iodomethylamine, difluoromethylamine,dichloromethylamine, dibromomethylamine, diiodomethylamine,trifluoromethylamine, trichloromethylamine, tribromomethylamine,triiodomethylamine, 2,2,2-trifluoroethylamine,2,2,2-trichloroethylamine, 2,2,2-tribromoethylamine,2,2,2-triiodoethylamine, 2,2,3,3,3-pentafluoropropylamine,2,2,3,3,3-pentachloropropylamine, 2,2,3,3,3-pentabromopropylamine,2,2,3,3,3-pentaiodopropylamine,2,2,2-trifluoro-1-trifluoromethylethylamine,2,2,2-trichloro-1-trichloromethylethylamine,2,2,2-tribromo-1-tribromomethylethylamine,2,2,2-triiodo-1-triiodomethylethylamine,1,1-bis(trifluoromethyl)-2,2,2-trifluoroethylamine,1,1-bis(trichloromethyl)-2,2,2-trichloroethylamine,1,1-bis(tribromoethyl)-2,2,2-tribromoethylamine,1,1-bis(triiodomethyl)-2,2,2-triiodoethylamine, 2-fluoroaniline,3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline,4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline,2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,6-difluoroaniline,3,5-difluoroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline,2,6-dibromoaniline, 3,5-dibromoaniline, 2,6-diiodoaniline,3,5-diiodoaniline, 2,4,6-trifluoroaniline, 2,4,6-trichloroaniline,2,4,6-tribromoaniline, 2,4,6-triiodoaniline, pentafluoroaniline,pentachloroaniline, pentabromoaniline, pentaiodoaniline,2-(trifluoromethyl) aniline, 3-(trifluoromethyl) aniline,4-(trifluoromethyl)aniline, 2,6-di(trifluoromethyl)aniline,3,5-di(trifluoromethyl)aniline and 2,4,6-tri(trifluoromethyl)aniline;more preferably water, hydrogen disulfide, methylamine, ethylamine,n-propylamine, isopropylamine, n-butylamine, sec-butylamine,tert-butylamine, isobutyl amine, n-octylamine, aniline, 2,6-xylylamine,2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine,trifluoromethylamine, pentafluoroethylamine, perfluoroproylamine,perfluorobutylamine, perfluoropentylamine, perfluorohexylamine,perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine,perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline,4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline,2,4,6-trifluoroaniline, pentafluoroaniline, 2,-(trifluoromethyl)aniline,3-(trifluoromethyl)aniline, 4-(trifluoromethyl)aniline,2,6-bis(trifluoromethyl)aniline, 3,5-bis(trifluoromethyl)aniline or2,4,6-tris(trifluoromethyl)aniline; in particular, preferably water,trifluoromethylamine, perfluorobutylamine, perfluorooctylamine,perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline,4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline,2,4,6-trifluoroaniline, pentafluoroaniline, 2-(trifluoromethyl)aniline,3-(trifluoromethyl) aniline, 4-(trifluoromethyl) aniline,2,6-bis(trifluoromethyl)aniline, 3,5-bis(trifluoromethyl)aniline and2,4,6-tris(trifluoromethyl)aniline; and most preferably water andpentafluoroaniline.

Further, as the compound (f) used for preparation of the compound [B],the followings and the like are mentioned.

The compound [A] is a compound obtained by contacting theabove-mentioned compounds (a), (b) and (c). The order of contacting thecompounds (a), (b) and (c) is not specifically limited, and for example,the following order can be adopted.

{circle around (1)} A method of contacting (c) after contacting (a) and(b).

{circle around (2)} A method of contacting (b) after contacting (a) and(c).

{circle around (3)} A method of contacting (a) after contacting (b) and(c).

The contact order is preferably {circle around (1)} or {circle around(2)}. Namely, the compound [A] is preferably a compound obtained bycontacting (c) with a contact product obtained by contacting (a) and(b), or a compound obtained by contacting (b) with a contact productobtained by contacting (a) and (c).

Further, the compound [B]is a compound obtained by contacting theabove-mentioned compounds (d), (e) and (f). The order of contacting thecompounds (d), (e) and (f) is not specifically limited, and for example,the following order can be adopted.

{circle around (1)}′ A method of contacting (f) after contacting (d) and(e).

{circle around (2)}′ A method of contacting (e) after contacting (d) and(f).

{circle around (3)}′ A method of contacting (d) after contacting (e) and(f).

The contact order is preferably {circle around (1)}′ or {circle around(2)}′. Namely, the compound [B] is preferably a compound obtained bycontacting (f) with a contact product obtained by contacting (d) and(e), or a compound obtained by contacting (e) with a contact productobtained by contacting (d) and (f).

The contact treatment in the preparation of the above-mentionedcompounds [A] and [B] is preferably carried out under an inert gasatmosphere. The treatment temperature is usually from −100° C. to 200°C., and preferably from −80° C. to 150° C. The treatment time is usuallyfrom 1 minute to 36 hours, and preferably from 10 minutes to 24 hours.Further, the treatment may use a solvent, and these compounds may bedirectly treated without using it. The solvent used is inert to the rawmaterial compounds (a), (b) and (c), or (d), (e) and (f).

Either of a non-polar solvent such as an aliphatic hydrocarbon solvent,an aromatic hydrocarbon solvent or the like, or a polar solvent such asan ethereal solvent or the like, can be used. Specific examples of thesolvent include butane, hexane, heptane, octane, 2,2,4-trimethylpentane,cyclohexane, benzene, toluene, xylene, dimethyl ether, diethyl ether,diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole,1,4-dioxane, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether,tetrahydrofuran, tetrahydropyran and the like.

In the present invention, a polar solvent is preferable among thesesolvents. As index representing the polarity of the solvent, E_(T) ^(N)value (C. Reichardt, “Solvents and Solvents Effects in OrganicChemistry”, 2nd ed., VCH Verlag (1988)) and the like are known, and inparticular, preferably, the polar solvent is a solvent which satisfiesthe expression:

E_(T) ^(N) of 0.5≦E_(T) ^(N)≧0.1

Examples of the polar solvent include ethereal solvents such as dimethylether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyltert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane,bis(2-methoxyethyl) ether, tetrahydrofuran, tetrahydropyran and thelike, and tetrahydrofuran is most preferable as the solvent.

The amounts used of the respective compounds in the preparation of thecompound [A] are not specifically limited. When the molar ratio of theamounts used of the respective compounds is defined as a molar ratio of(a):(b):(c)=1:y¹:z¹, it is preferable that y¹ and z¹ satisfysubstantially the expression (1):

c=y ¹+2z ¹  (1)

(wherein c represents a valence of M¹ in the expression (1)).

y¹ in the expression (1) is preferably a numeral of from 0.01 to 1.99,more preferably a numeral of from 0.20 to 1.80, further preferably anumeral of from 0.25 to 1.50, and most preferably a numeral of from 0.50to 1.00. z¹ in the expression (1) is a numeral determined by c,y¹ andthe expression (1).

Further, the amount used of the respective compounds is not alsospecifically limited in the preparation of the compound [B]. When themolar ratio of the amounts used of the respective compounds is definedas a molar ratio of (d):(e):(f)=x¹:y²:z² it is preferable that x¹, y²and z² satisfy substantially the expression (2) when J in the generalformula [6] is an atom of Group XVI, and the expression (3) when J inthe general formula [6] is an atom of Group XV:

d×x ¹ =y ² +f×z ²  (2)

y ² +f×z ² ≦d×x ¹ ≦y ²+2×f×z ²  (3)

(wherein each of d and f in the expressions (2) and (3) is the samevalue as in the above-mentioned general formula [4] or [6],respectively.)

y² in the expressions (2) and (3) is preferably a numeral of y²/x¹ offrom 0.01 to 1.99, more preferably a numeral of from 0.2 to 1.8, furtherpreferably a numeral of from 0.25 to 1.5, and most preferably a numeralof from 0.5 to 1.0. z² in the expressions (2) or (3) is a numeraldetermined by d, f, x¹, y² and the above-mentioned expression (2) or(3). Further, x¹ is a numeral being an arbitrary positive value.

Even if the use of the respective compounds are really designed so as toperfectly satisfy the above-mentioned expressions (1) to (3) in thecontact treatment of the above-mentioned compounds, the amounts used mayfluctuate finely, and it is usually carried out to appropriatelyincrease and decrease the amounts used to a certain degree consideringthe amount of a compound which remains while being unreacted. Herein,“satisfy substantially” means that a case of designing to obtain acompound obtained by contacting the respective compounds at the molarratio satisfying the above-mentioned expressions is included even if theabove-mentioned expressions is not perfectly satisfied.

When the molar ratio of the amounts used of the respective compounds isdefined as a molar ratio of (a):(b):(c)=1:y¹:z¹ in the preparation ofthe compound [A], it is preferable that y¹ and z¹ satisfy the expression(4):

0≦|c−y ¹−2 z ¹|≦0.2  (4)

(c represents a valence of M¹ in the expression (4)).

Further, when the molar ratio of the amounts used of the respectivecompounds is defined as a molar ratio of (d):(e):(f)=x¹:y²:z² in thepreparation of the compound [B], it is preferable that x¹, y² and z²satisfy the expression (5) when J in the general formula [6] is an atomof Group XVI:

0≦|d−(y ² +f×z ²)÷x ¹|≦0.2  (5)

(each of d and f in the expression (5) is the same value as in theabove-mentioned formula [4] or [6].)

As a result of the contact treatment, at least one of (a), (b) and (c)or at least one of (d), (e) and (f) which are raw materials may remainas unreacted matters concerning the compounds.

Further, it is preferable in the preparation of the compound [A] todistill the solvent from the product after the contact treatment andcarry out drying at 25° C. or more for one hour or more under reducedpressure. It is more preferable to carry out drying at 60 to 200° C. forone to 24 hours and most preferable at 80 to 160° C. for 4 to 18 hours.

Specific example of the production process of the compound [A] is shownbelow in detail when M¹ is zinc atom, the compound (b) ispentafluorophenol, and the compound (c) is water. A process whichinclude the following steps can be adopted:

Tetrahydrofuran is used as a solvent; a hexane solution of diethylzincis added thereto and cooled to 0° C.; pentafluorophenol of the equimolaramount to diethylzinc is added dropwise thereto; after stirring at roomtemperature for 10 minutes to 24 hours, 0.5-fold molar amount of waterto diethylzinc is further added dropwise; after stirring at roomtemperature for 10 minutes to 24 hours, the solvent is removed bydistillation; and drying is carried out at 120° C. for 8 hours underreduced pressure.

Of course, the compounds used in these treatments are not limited topentafluorophenol and water, the compound as a raw material is notlimited to a zinc compound, and the condition at drying is not limitedto at 120° C. for 8 hours.

Further, a specific example of the production process of the compound[B] is shown below in detail when M² is zinc atom, the compound (e) ispentafluorophenol, and the compound (f) is 1,3-cyclopentanediol(amixture of cis-isomer and trans-isomer).

A process which include the following steps can be adopted:

A hexane solution of diethylzinc and toluene are charged in a flaskwhose atmosphere was replaced with argon and the mixture is stirred andcooled at −78° C.; a hexane solution of pentafluorophenol which is anequimolar amount to diethylzinc is added thereto dropwise and theresultant was stirred at room temperature for 1 hour; thereafter,0.5-fold molar amount of 1,3-cyclopentanediol (a mixture of cis-isomerand trans-isomer) to diethylzinc is further added dropwise and stirringis carried out overnight; and then, a volatile material is removed bydistillation and a solid prepared is dried at room temperature underreduced pressure.

Of course, the compound used in these treatments is not limited topentafluorophenol and 1,3-cyclopentanediol (a mixture of cis-isomer andtrans-isomer), and the metal compound as a raw material is not limitedto a zinc compound.

Next, the compound [C] represented by the general formula [7] isillustrated.

M³ has been already described.

T³ in the general formula [7] represents an atom of the Group XIV, GroupXV or Group XVI of the Periodic Table of the Elements (Revised editionof IUPAC Inorganic Chemistry Nomenclature 1989), and when a pluralnumber of T³'s exist, they may be mutually the same or different.Specific example of the atom of the Group XIV includes a carbon atom, asilicon atom and the like, specific example of the atom of the Group XVincludes a nitrogen atom, a phosphorous atom and the like, and specificexample of the atom of the Group XVI includes an oxygen atom, a sulfuratom and the like. T³ is preferably a carbon atom, a nitrogen atom or anoxygen atom, further preferably a nitrogen atom or an oxygen atom, andin particular, T³ is preferably an oxygen atom.

“s” in the general formula [7] represents a valence of T³. When T³ isthe atom of the Group XIV, “s” is 4, when T is the atom of Group XV, “s”is 3, and when T³ is the atom of Group XVI, “s” is 2.

R⁵ in the general formula [7] represents an electron-withdrawing groupor a group containing an electron-withdrawing group, and when a pluralnumber of R⁵'s exist, they may be mutually the same or different.Examples of the electron-withdrawing group or the group containing anelectron-withdrawing group are selected from those already described inthe illustration of R₁ and R³, and the preferable group is the samegroup as in R¹ and R³.

Further, R⁶ represents a hydrocarbon group, and a plural number of R⁶'smay be mutually the same or different. The hydrocarbon group in R⁶ ispreferably an alkyl group, an aryl group or an aralkyl group.

As the alkyl group herein, an alkyl group having 1 to 20 carbon atoms ispreferable. Examples include a methyl group, an ethyl group, a n-propylgroup, an isopropyl group, a n-butyl group, a sec-butyl group, atert-butyl group, an isobutyl group, a n-pentyl group, a neopentylgroup, a n-hexyl group, a n-octyl group, a n-decyl group, a n-dodecylgroup, a n-pentadecyl group, a n-eicosyl group, and the like. A methylgroup, an ethyl group, an isopropyl group, a tert-butyl group or anisobutyl group is more preferable.

Any one of these alkyl groups may be substituted with a halogen atomsuch as a fluorine atom, a chlorine atom, a bromine atom or an iodineatom. Examples of the alkyl group having 1 to 20 carbon atoms which issubstituted with the halogen atom include a fluoromethyl group, adifluoromethyl group, a trifluoromethyl group, a chloromethyl group, adichloromethyl group, a trichloromethyl group, a bromomethyl group, adibromomethyl group, a tribromomethyl group, an iodomethyl group, adiiodomethyl group, a triiodomethyl group, a fluoroethyl group, adifluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, apentafluoroethyl group, a chloroethyl group, a dichloroethyl group, atrichloroethyl group, a tetrachloroethyl group, a pentachloroethylgroup, a bromoethyl group, a dibromoethyl group, a tribromoethyl group,a tetrabromoethyl group, a pentabromoethyl group, a perfluoropropylgroup, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexylgroup, a perfluorooctyl group, a perfluorododecyl group, aperfluoropentadecyl group, a perfluoroeicosyl group, a perchloropropylgroup, a perchlorobutyl group, a perchloropentyl group, a perchlorohexylgroup, a perchlorooctyl group, a perchlorododecyl group, aperchloropentadecyl group, a perchloroeicosyl group, a perbromopropylgroup, a perbromobutyl group, a perbromopentyl group, a perbromohexylgroup, a perbromooctyl group, a perbromododecyl group, aperbromopentadecyl group, a perbromoeicosyl group and the like.

Further, any one of these alkyl groups may be partially substituted withan alkoxy group such as a methoxy group, an ethoxy group or the like, anaryloxy group such as a phenoxy group or the like, or an aralkyloxygroup such as a benzyloxy group or the like, etc.

As the aryl group, an aryl group having 6 to 20 carbon atoms ispreferable. Examples thereof include a phenyl group, a 2-tolyl group, a3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylylgroup, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a3,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a2,3,4,6-tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, apentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group,an isopropylphenyl group, a n-butylphenyl group, a sec-butylphenylgroup, a tert-butylphenyl group, a n-pentylphenyl group, aneopentylphenyl group, a n-hexylphenyl group, a n-octylphenyl group, an-decylphenyl group, a n-dodecylphenyl group, a n-tetradecylphenylgroup, a naphthyl group, an anthracenyl group and the like, and a phenylgroup is more preferable.

Any one of these aryl groups may be partially substituted with a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom or aniodine atom, an alkoxy group such as a methoxy group, an ethoxy group orthe like, an aryloxy group such as a phenoxy group or the like, or anaralkyloxy group such as a benzyloxy group or the like, etc.

As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms ispreferable. Examples include a benzyl group, a (2-methylphenyl)methylgroup, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a(2,3-dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a(2,5-dimethylphenyl)methyl group, a (2,6-dimethylphenyl)methyl group, a(3,4-dimethylphenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a(2,3,4-timethylphenyl)methyl group, a (2,3,5-timethylphenyl)methylgroup, a (2,3,6-timethylphenyl)methyl group, a(3,4,5-timethylphenyl)methyl group, a (2,4,6-timethylphenyl)methylgroup, a (2,3,4,5-tetramethylphenyl)methyl group, a(2,3,4,6-tetramethylphenyl)methyl group, a(2,3,5,6-tetramethylphenyl)methyl group, a (pentamethylphenyl)methylgroup, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, an(isopropylphenyl)methyl group, a (n-butylphenyl)methyl group, a(sec-butylphenyl)methyl group, a (tert-butylphenyl)methyl group, a(n-pentylphenyl)methyl group, a (neopentylphenyl)methyl group, a(n-hexylphenyl)methyl group, a (n-octylphenyl)methyl group, a(n-decylphenyl)methyl group, a (n-dodecylphenyl)methyl group, a(n-tetradecylphenyl)methyl group, a naphthylmethyl group, ananthracenylmethyl group and the like, and a benzyl group is morepreferable.

Any one of these aryl groups may be partially substituted with a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom or aniodine atom, an alkoxy group such as a methoxy group, an ethoxy group orthe like, an aryloxy group such as a phenoxy group or the like, or anaralkyloxy group such as a benzyloxy group or the like, etc.

R⁶ in the general formula [7] is preferably an aryl group or an alkylgroup.

“h” in the general formula [7] represents a numeral of 1 or more, andusually an integer. “h” is preferably an integer of 1 to 5, and inparticular, 1.

The compound represented by the general formula [7] is preferably aμ-oxo-bis(alkylzinc) or μ-oxo-bis(arylzinc), in particular.

Two or more of molecules of the compound represented by the generalformula [7] may be associated.

The production process of the compound represented by the generalformula [7] is not specifically limited, and for example, a process oftreating an organometallic compound such as an alkylmetal, a halogenatedalkylmetal or the like with a compound selected from agem-dihalogenohydrocarbon, a silane, a germane, an amine, a phosphine,water, a hydrate of metal salt, hydrogen disulfide and the like, ismentioned.

The treatment is preferably carried out under inert gas atmosphere. Thetreatment temperature is usually from −100° C. to 200° C., andpreferably from −80° C. to 150° C. The treatment time is usually from 1minute to 36 hours, and preferably from 10 minutes to 24 hours. Further,the treatment may use a solvent, and these compounds may be directlytreated without using it. The solvent used is preferably an aliphatichydrocarbon solvent, an aromatic hydrocarbon solvent or an etherealsolvent which is inert to an organometallic compound such as analkylmetal, a halogenated alkylmetal or the like and a compound selectedfrom a gem-dihalogenohydrocarbon, a silane, a germane, an amine, aphosphine, water, a hydrate of metal salt, hydrogen disulfide and thelike. Specific examples of the solvent include butane, hexane, heptane,octane, benzene, toluene, diethyl ether, di-n-butyl ether,tetrahydrofuran and the like.

Further, in the treatment, the order of dropwise addition of thecompound selected from a gem-dihalogenohydrocarbon, a silane, a germane,an amine, a phosphine, water, a hydrate of metal salt, hydrogendisulfide and the like is not specifically limited, it may besuccessively dropwise added, may be simultaneously dropwise added, and 2or more of solvents may be dropwise added after mixing. Arbitraryamounts of R⁵ and R⁶ can be introduced by adjusting the molar number ofthe compound selected from a gem-dihalogenohydrocarbon, a silane, agermane, an amine, a phosphine, water, a hydrate of metal salt, hydrogendisulfide and the like to the organometallic compound.

Further, as a result of the treatment, the organometallic compound beinga raw material and the compound selected from agem-dihalogenohydrocarbon, a silane, a germane, an amine, a phosphine,water, a hydrate of metal salt, hydrogen disulfide and the like mayremain as an unreacted matter. The compound represented by the generalformula [7] which was obtained by the treatment can be used as acatalyst component for addition polymerization after separation andpurification such as recrystallization or the like, but the reactedsolution can be also used as a catalyst component for additionpolymerization. The solvent is preferably removed by distillation fromthe reacted solution, and drying is preferably carried out at atemperature of 25° C. or more for 1 hour or more under reduced pressure.It is more preferable to carry out drying at 60 to 200° C. for one to 24hours, and most preferable at 80 to 160° C. for 4 to 18 hours.

Specific example of the production process of the compound representedby the general formula [7] is further shown below in detail when M³ iszinc atom and a treating agent is water.

A process that toluene is a solvent, a hexane solution of a dialkylzinc(for example, diethylzinc) is added thereto and cooled at 0° C., waterof an equimolar amount to the dialkylzinc is added dropwise, and themixture is stirred at room temperature for 10 minutes to 24 hours, canbe adopted. Of course, those used in these treatments are not limited tothe dialkylzinc and water.

Then, the compound [D] represented by the general formula [8] isillustrated.

M⁴ has been already described.

As X¹, specific examples of the atom of the Group XIV as X¹ include acarbon atom, a silicon atom and the like, specific examples of the atomof Group the XV include a nitrogen atom, a phosphorous atom and thelike, and specific examples of the atom of the Group XVI include anoxygen atom, a sulfur atom and the like. X¹ is preferably a carbon atom,a nitrogen atom or an oxygen atom, further preferably a nitrogen atom oran oxygen atom, and in particular, X¹ is preferably an oxygen atom.

“i” in the general formula [8] represents a numeral by 1 smaller than avalence of X¹. When X¹ is the atom of the Group XIV, “i” is 3, when X¹is the atom of the Group XV, “i” is 2, and when X¹ is the atom of theGroup XIV, “i” is 1.

R⁷ in the general formula [8] represents an electron-withdrawing groupor a group containing an electron-withdrawing group, and when a pluralnumber of R⁷'s exist, they may be mutually the same or different. Theexamples of the electron-withdrawing group or the group containing anelectron-withdrawing group are selected from those already described inthe illustration of R¹ and R³, and the preferable group is the samegroup as in R¹ and R³.

Specific examples of X¹R⁷i which is a combination of X¹ and R⁷ when X¹is a carbon atom, include a tri(fluoromethyl)methyl group, atri(chloromethyl)methyl group, a tri(bromomethyl)methyl group, atri(iodomethyl)methyl group, a tri(difluoromethyl)methyl group, atri(dichloromethyl)methyl group, a tri(dibromomethyl)methyl group, atri(diiodomethyl)methyl group, a tri(trifluoromethyl)methyl group, atri(trichloromethyl)methyl group, a tri(tribromomethyl)methyl group, atri(triiodomethyl)methyl group, a tri(2,2,2-trifluoromethyl)methylgroup, a tri(2,2,2-trichloromethyl)methyl group, atri(2,2,2-tribromomethyl)methyl group, a tri(2,2,2-triiodomethyl)methylgroup, a tri(2,2,3,3,3-pentafluoropropyl)methyl group, atri(2,2,3,3,3-pentachloropropyl)methyl group, atri(2,2,3,3,3-pentabromopropyl)methyl group, atri(2,2,3,3,3-pentaiodopropyl)methyl group, atri(2,2,2-trifluoro-1-trifluoromethylethyl)methyl group, atri(2,2,2-trichloro-1-trichloromethylethyl)methyl group, atri(2,2,2-tribromo-1-tribromomethylethyl)methyl group, atri(2,2,2-triiodo-1-triiodomethylethyl)methyl group, atri(1,1-di(trifluoromethyl)-2,2,2-trifluoroethyl)methyl group, atri(1,1-di(trichloromethyl)-2,2,2-trichloroethyl)methyl group, atri(1,1-di(tribromomethyl)-2,2,2-tribromoethyl)methyl group, atri(1,1-di(triiodomethyl)-2,2,2-triiodoethyl)methyl group, atri(2-fluorophenyl)methyl group, a tri(3-fluorophenyl)methyl group, atri(4-fluorophenyl)methyl group, a tri(2-chlorophenyl)methyl group, atri(3-chlorophenyl)methyl group, a tri(4-chlorophenyl)methyl group, atri(2-bromophenyl)methyl group, a tri(3-bromophenyl)methyl group, atri(4-bromophenyl)methyl group, a tri(2-iodophenyl)methyl group, atri(3-iodophenyl)methyl group, a tri(4-iodophenyl)methyl group, atri(2,6-difluorophenyl)methyl group, a tri(3,5-difluorophenyl)methylgroup, a tri(2,6-dichlorophenyl)methyl group, atri(3,5-dichlorophenyl)methyl group, a tri(2,6-dibromophenyl)methylgroup, a tri(3,5-dibromophenyl)methyl group, atri(2,6-diiodophenyl)methyl group, a tri(3,5-diiodophenyl)methyl group,a tri(2,4,6-trifluorophenyl)methyl group, atri(2,4,6-trichlorophenyl)methyl group, atri(2,4,6-tribromophenyl)methyl group, a tri(2,4,6-triiodophenyl)methylgroup, a tri(pentafluorophenyl)methyl group, atri(pentachlorophenyl)methyl group, a tri(pentabromophenyl)methyl group,a tri(pentaiodophenyl)methyl group, atri(3-(trifluoromethyl)phenyl)methyl group, atri(4-(trifluoromethyl)phenyl)methyl group, atri(2,6-di(trifluoromethyl)phenyl)methyl group, atri(3,5-di(trifluoromethyl)phenyl)methyl group, atri(2,4,6-tri(trifluoromethyl)phenyl)methyl group, atri(2-cyanophenyl)methyl group, a tri(3-cyanophenyl)methyl group, atri(4-cyanophenyl)methyl group, a tri(2-nitrophenyl)methyl group, atri(3-nitrophenyl)methyl group, a tri(4-nitrophenyl)methyl group and thelike. Further, functional groups obtained by substituting X from carbonatom to silicon atom, and functional groups represented by replacing amethyl group in the above-mentioned specific examples with a silylgroup, can be also exemplified.

Similarly, specific examples of X¹R⁷i when X¹ is a nitrogen atom,include a di(fluoromethyl)amino group, a di(chloromethyl)amino group, adi(bromomethyl)amino group, a di(iodomethyl)amino group, adi(difluoromethyl)amino group, a di(dichloromethyl)amino group, a di(dibromomethyl) amino group, a di (diiodomethyl) amino group, adi(trifluoromethyl)amino group, a di(trichloromethyl)amino group, adi(tribromomethyl)amino group, a di(triiodomethyl)amino group, adi(2,2,2-trifluoroethyl)amino group, a di(2,2,2-trichloroethyl)aminogroup, a di(2,2,2-tribromoethyl)amino group, adi(2,2,2-di(triiodoethyl)amino group, adi(2,2,3,3,3-pentafluoropropyl)amino group, adi(2,2,3,3,3-pentachloropropyl)amino group, adi(2,2,3,3,3-pentabromopropyl)amino group, adi(2,2,3,3,3-pentaiodopropyl)amino group, adi(2,2,2-trifluoro-1-trifluoromethylethyl)amino group, adi(2,2,2-trichloro-1-trichloromethylethyl)amino group, adi(2,2,2-tribromo-1-tribromomethylethyl)amino group, adi(2,2,2-triiodo-1-triiodomethylethyl)amino group, adi(1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl)amino group, adi(1,1-di(trichloromethyl)-2,2,2-trichloroethyl)amino group, adi(1,1-di(tribromomethyl)-2,2,2-tribromoethyl)amino group, adi(1,1-di(triiodomethyl)-2,2,2-triiodoethyl)amino group, adi(2-fluorophenyl)amino group, a di(3-fluorophenyl)amino group, adi(4-fluorophenyl)amino group, a di(2-chlorophenyl)amino group, adi(3-chlorophenyl)amine, a di(4-chlorophenyl)amino group, adi(2-bromophenyl) amino group, a di(3-bromophenyl) amino group, adi(4-bromophenyl)amino group, a di(2-iodophenyl)amino group, adi(3-iodophenyl)amino group, a di(4-iodophenyl)amino group, adi(2,6-difluorophenyl)amino group, a di(3,5-difluorophenyl)amino group,a di(2,6-dichlorophenyl)amino group, a di(3,5-dichlorophenyl)aminogroup, a di(2,6-dibromophenyl)amino group, a di(3,5-dibromophenyl)aminogroup, a di(2,6-diiodophenyl)amino group, a di(3,5-diiodophenyl)aminogroup, a di(2,4,6-trifluorophenyl)amino group, adi(2,4,6-trichlorophenyl)amino group, a di(2,4,6-tribromophenyl)aminogroup, a di(2,4,6-triiodophenyl)amino group, adi(pentafluorophenyl)amino group, a di(pentachlorophenyl)amino group, adi(pentabromophenyl)amino group, a di(pentaiodophenyl)amino group, adi(2-(trifluoromethyl)phenyl)amino group, adi(3-(trifluoromethyl)phenyl)amino group, adi(4-(trifluoromethyl)phenyl)amino group, adi(2,6-di(trifluoromethyl)phenyl)amino group, adi(3,5-di(trifluoromethyl)phenyl)amino group, adi(2,4,6-tri(trifluoromethyl)phenyl)amino group, adi(2-cyanophenyl)amino group, a di(3-cyanophenyl)amino group, adi(4-cyanophenyl)amino group, a di(2-nitrophenyl)amino group, adi(3-nitrophenyl)amino group, a di(4-nitrophenyl)amino group, and thelike.

Further, a functional group obtained by substituting X from nitrogenatom to phosphorous atom, and a functional group represented byreplacing an amino group in the above-mentioned specific example with aphosphino group can be also exemplified.

Further, specific examples, when X¹ is an oxygen atom, include afluoromethoxy group, a chloromethoxy group, a bromomethoxy group, aniodomethoxy group, a difluoromethoxy group, a dichloromethoxy group, adibromomethoxy group, a diiodomethoxy group, a trifluoromethoxy group, atrichloromethoxy group, a tribromomethoxy group, a triiodomethoxy group,a 2,2,2-trifluoroethoxy group, a 2,2,2-trichloroethoxy group, a2,2,2-tribromoethoxy group, a 2,2,2-triiodoethoxy group, a2,2,3,3,3-pentafluoropropoxy group, a 2,2,3,3,3-pentachloropropoxygroup, a 2,2,3,3,3-pentabromopropoxy group, a 2,2,3,3,3-pentaiodopropoxygroup, a 2,2,2-trifluoro-1-trifluoromethylethoxy group, a2,2,2-trichloro-1-trichloromethylethoxy group, a2,2,2-tribromo-1-tribromomethylethoxy group, a2,2,2-triiodo-1-triiodomethylethoxy group, a1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxy group, a1,1-di(trichloromethyl)-2,2,2-trichloroethoxy group, a1,1-di(tribromomethyl)-2,2,2-tribromoethoxy group, a1,1-di(triiodomethyl)-2,2,2-triiodoethoxy group, a 2-fluorophenoxygroup, a 3-fluorophenoxy group, a 4-fluorophenoxy group, a2-chlorophenoxy group, a 3-chlorophenoxy group, a 4-chlorophenoxy group,a 2-bromophenoxy group, a 3-bromophenoxy group, a 4-bromophenoxy group,a 2-iodophenoxy group, a 3-iodophenoxy group, a 4-iodophenoxy group, a2,6-difluorophenoxy group, a 3,5-difluorophenoxy group, a3,4,5-trifluorophenoxy group, a 2,6-dichlorophenoxy group, a3,5-dichlorophenoxy group, a 2,6-dibromophenoxy group, a3,5-dibromophenoxy group, a 2,6-diiodophenoxy group, a 3,5-diiodophenoxygroup, a 2,4,6-trifluorophenoxy group, a 2,4,6-trichlorophenoxy group, a2,4,6-tribromophenoxy group, a 2,4,6-triiodophenoxy group, apentafluorophenoxy group, a pentachlorophenoxy group, apentabromophenoxy group, a pentaiodophenoxy group, a2-(trifluoromethyl)phenoxy group, a 3-(trifluoromethyl)phenoxy group, a4-(trifluoromethyl)phenoxy group, a 2,6-di(trifluoromethyl)phenoxygroup, a 3,5-di(trifluoromethyl)phenoxy group, a 2,4,6-tri(trifluoromethyl) phenoxy group, a 2-cyanophenoxy group, a3-cyanophenoxy group, a 4-cyanophenoxy group, a 2-nitrophenoxy group, a3-nitrophenoxy group, a 4-nitrophenoxy group and the like. Further, afunctional group obtained by substituting X from oxygen atom to sulfuratom, and a functional group represented by replacing an oxy group inthe above-mentioned specific example with a thioxy group can be alsoexemplified.

X¹R⁷i is preferably a tri(fluoroalkyl)methyl group, atri(fluoroaryl)methyl group, a di(fluoroalkyl)amino group, adi(fluoroaryl)amino group, a fluoroalkyloxy group or a fluoroaryloxygroup, such as a tri(fluoromethyl)methyl group, atri(pentafluorophenyl)methyl group, a di(fluoromethyl) amino group, adi(pentafluorophenyl) amino group, a trifluoromethoxy group, a2,2,2-trifluoro-1-trifluoromethylethoxy group, a1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxy group, a3,4,5-trifluorophenoxy group, or a pentafluorophenoxy group, morepreferably a fluoroalkyloxy group or a fluoroaryloxy group such as a2,2,2-trifluoro-1-trifluoromethylethoxy group, a1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxy group, a3,4,5-trifluorophenoxy group, or a pentafluorophenoxy group.

R⁸ in the general formula [8] represents a hydrogen atom, a halogen atomor a hydrocarbon group. Specific examples of the halogen atom in R⁸include a fluorine atom, a chlorine atom, a bromine atom and an iodineatom. As a hydrocarbon group in R⁸, an alkyl group, an aryl group or anaralkyl group is preferable. Specific examples thereof include the samecompounds as in R⁶ in the general formula [7] as described above.

R⁸ in the general formula [8] is preferably an alkyl group or an arylgroup, and more preferably an alkyl group, and “t” represents a numeralsatisfying 0<t≦j. “t” is preferably the same numeral as “j”.

Two or more of molecules of the compound represented by the generalformula [8] may be associated.

Among the compound represented by the general formula [8], specificexamples of a case in which M is a zinc atom, includetrifluoromethoxy(trimethylsiloxy)zinc,trifluoromethoxy(triethylsiloxy)zinc,trifluoromethoxy(triphenylsiloxy)zinc,2,2,2-trifluoroethoxy(trimethylsiloxy)zinc,2,2,2-trifluoroethoxy(triethylsiloxy)zinc,2,2,2-trifluoroethoxy(triphenylsiloxy)zinc,1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxy(trimethylsiloxy)zinc,1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxy(triethylsiloxy)zinc,1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxy(triphenylsiloxy)zinc,2,2,2-trifluoro-1-trifluoromethylethoxy(trimethylsiloxy)zinc,2,2,2-trifluoro-1-trifluoromethylethoxy(triethylsiloxy)zinc,2,2,2-trifluoro-1-trifluoromethylethoxy(triphenylsiloxy)zinc,2,2,2,3,3,3-pentafluoropropoxy(trimethylsiloxy)zinc,2,2,2,3,3,3-pentafluoropropoxy(triethylsiloxy)zinc,2,2,2,3,3,3-pentafluoropropoxy(triphenylsiloxy)zinc,2,4,6-trifluorophenoxy(trimethylsiloxy)zinc,2,4,6-trifluorophenoxy(triethylsiloxy)zinc,2,4,6-trifluorophenoxy(triphenylsiloxy)zinc,3,4,5-trifluorophenoxy(trimethylsiloxy)zinc,3,4,5-trifluorophenoxy(triethylsiloxy)zinc,3,4,5-trifluorophenoxy(triphenylsiloxy)zinc,pentafluorophenoxy(trimethylsiloxy)zinc,pentafluorophenoxy(triethylsiloxy)zinc,pentafluorophenoxy(triphenylsiloxy)zinc,4-trifluoromethylphenoxy(trimethylsiloxy)zinc,4-trifluoromethylphenoxy(triethylsiloxy)zinc,4-trifluoromethylphenoxy(triphenylsiloxy)zinc,trifluoromethylamido(trimethylsiloxy)zinc,trifluoromethylamido(triethylsiloxy)zinc,trifluoromethylamido(triphenylsiloxy)zinc,2,2,2-trifluoroethylamido(trimethylsiloxy)zinc,2,2,2-trifluoroethylamido(triethylsiloxy)zinc,2,2,2-trifluoroethylamido(triphenylsiloxy)zinc,pentafluoroanilido(trimethylsiloxy)zinc,pentafluoroanilido(triethylsiloxy)zinc,pentafluoroanilido(triphenylsiloxy)zinc, n-trifluoromethylanilido(trimethylsiloxy)zinc, n-trifluoromethylanilido(triethylsiloxy)zinc,n-trifluoromethylanilido(triphenylsiloxy)zinc,trichloromethoxy(trimethylsiloxy)zinc,trichloromethoxy(triethylsiloxy)zinc,trichloromethoxy(triphenylsiloxy)zinc,2,2,2-trichloroethoxy(trimethylsiloxy)zinc,2,2,2-trichloroethoxy(triethylsiloxy)zinc,2,2,2-trichloroethoxy(triphenylsiloxy)zinc,1,1-di(trichloromethyl)-2,2,2-trichloroethoxy(trimethylsiloxy)zinc,1,1-di(trichloromethyl)-2,2,2-trichloroethoxy(triethylsiloxy)zinc,1,1-di(trichloromethyl)-2,2,2-trichloroethoxy(triphenylsiloxy)zinc,2,2,2-trichloro-m-trichloromethylethoxy(trimethylsiloxy)zinc,2,2,2-trichloro-1-trichloromethylethoxy(triethylsiloxy)zinc,2,2,2-trichloro-1-trichloromethylethoxy(triphenylsiloxy)zinc,2,2,3,3,3-pentachloropropoxy(trimethylsiloxy)zinc,2,2,3,3,3-pentachloropropoxy(triethylsiloxy)zinc,2,2,3,3,3-pentachloropropoxy(triphenylsiloxy)zinc,2,4,6-trichlorophenoxy(trimethylsiloxy)zinc,2,4,6-trichlorophenoxy(triethylsiloxy)zinc,2,4,6-trichlorophenoxy(triphenylsiloxy)zinc,pentachlorophenoxy(trimethylsiloxy)zinc,pentachlorophenoxy(triethylsiloxy)zinc,pentachlorophenoxy(triphenylsiloxy)zinc,4-trichloromethylphenoxy(trimethylsiloxy)zinc,4-trichloromethylphenoxy(triethylsiloxy)zinc,4-trichloromethylphenoxy(triphenylsiloxy)zinc, trichloromethylamido(trimethylsiloxy)zinc, trichloromethylamido(triethylsiloxy)zinc,trichloromethylamido(triphenylsiloxy)zinc,2,2,2-trichloroethylamido(trimethylsiloxy)zinc,2,2,2-trichloroethylamido(triethylsiloxy)zinc,2,2,2-trichloroethylamido(triphenylsiloxy)zinc,pentachloroanilido(trimethylsiloxy)zinc,pentachloroanilido(triethylsiloxy)zinc,pentachloroanilido(triphenylsiloxy)zinc,n-trichloromethylanilido(trimethylsiloxy)zinc,n-trichloromethylanilido(triethylsiloxy)zinc,n-trichloromethylanilido(triphenylsiloxy)zinc,bis(trifluoromethoxy)zinc, bis(2,2,2-trifluoroethoxy)zinc,bis(1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxy)zinc,bis(2,2,2-trifluoro-1-trifluoromethylethoxy)zinc,bis(2,2,3,3,3-pentafluoropropoxy)zinc, bis(2,4,6-trifluorophenoxy)zinc,bis(3,4,5-trifluorophenoxy)zinc, bis(pentafluorophenoxy)zinc,bis(4-trifluoromethylphenoxy)zinc, bis(trifluoromethylamido)zinc,bis(pentafluoroanilido)zinc, bis(N-trifluoromethylanilido)zinc,trifluoromethoxyzinc methyl, 2,2,2-trifluoroethoxyzinc methyl,1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxyzinc methyl,2,2,2-trifluoro-1-trifluoromethylethoxyzinc methyl,2,2,3,3,3-pentafluoropropoxyzinc methyl, 2,4,6-trifluorophenoxyzincmethyl, 3,4,5-trifluorophenoxyzinc methyl, pentafluorophenoxyzincmethyl, 4-trifluoromethylphenoxyzinc methyl, 4-trifluoromethylamidozincmethyl, 2,2,2-trifluoroethylamidozinc methyl, pentafluoroanilidozincmethyl, n-trifluoromethylanilidozinc methyl, trifluoromethoxyzinc ethyl,2,2,2-trifluoroethoxyzinc ethyl,1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxyzinc ethyl,2,2,2-trifluoro-1-trifluoromethylethoxyzinc ethyl,2,2,3,3,3-pentafluoropropoxyzinc ethyl, 2,4,6-trifluorophenoxyzincethyl, 3,4,5-trifluorophenoxyzinc ethyl, pentafluorophenoxyzinc ethyl,4-trifluoromethylphenoxyzinc ethyl, 4-trifluoromethylamidozinc ethyl,2,2,2-trifluoroethylamidozinc ethyl, pentafluoroanilidozinc ethyl,N-trifluoromethylanilidozinc ethyl and the like.

In particular, the compound represented by the general formula [8] ispreferably a bis(fluoroalkyloxy)zinc or a bis(fluoroaryloxy)zinc, andmost preferably bis(2,2,2-trifluoro-1-trifluoromethylethoxy)zinc,bis(3,4,5-trifluorophenoxy) zinc, bis (pentafluorophenoxy) zinc orbis(1,1-di(trifluoromethyl)-2,2,2-trifluoroethoxy)zinc.

The production process of the compound represented by theabove-mentioned general formula [8] is not specifically limited, and forexample, a process of treating an organometallic compound such as analkylmetal, a halogenated alkylmetal or the like with a compoundrepresented by LiX¹R⁷i such as an alkyloxylithium compound having anelectron-withdrawing substituent, an aryloxylithium compound having anelectron-withdrawing substituent, an aminolithium compound having anelectron-withdrawing substituent or the like, or a compound representedby HX¹R⁷i such as an alcohol having an electron-withdrawing substituent,a phenol having an electron-withdrawing substituent, an amine having anelectron-withdrawing substituent or the like, is mentioned.

The treatment is preferably carried out under inert gas atmosphere. Thetreatment temperature is usually from −80° C. to 200° C., and preferablyfrom −5° C. to 120° C. The treatment time is usually from 1 minute to 36hours, and preferably from 10 minutes to 24 hours. Further, thetreatment may use a solvent, and these compounds may be directly treatedwithout using it. The solvent used is preferably an aliphatichydrocarbon solvent, an aromatic hydrocarbon solvent or an etherealsolvent which is inert to the organometallic compound, the compoundrepresented by LiX¹R⁷i, the compound represented by HX¹R⁷i and the like.

Specific examples of the solvent is the same examples as specificallymentioned in the item of the compound [A].

Further, in the treatment, the order of dropwise addition of theorganometallic compound, the compound represented by LiX¹R⁷i and thecompound represented by HX¹R⁷i is not specifically limited, it may besuccessively dropwise added, may be simultaneously dropwise added, and 2or more of solvents may be dropwise added after mixing. Arbitraryamounts of (X¹R⁷i) and R⁸ can be introduced by adjusting the molarnumber of the compound represented by LiX¹R⁷i and the compoundrepresented by HX¹R⁷i to the organometallic compound. Further, as aresult of the treatment, the organometallic compound being a rawmaterial, the compound represented by LiX¹R⁷i, the compound representedby HX¹R⁷i and the like, may remain as unreacted matters. The compoundrepresented by the general formula [8], which was obtained by thetreatment can be used as a catalyst for addition polymerization afterseparation and purification such as recrystallization or the like, butthe reacted solution can be also used as a catalyst component foraddition polymerization. The solvent is preferably removed bydistillation from the reacted solution, and drying is preferably carriedout at a temperature of 25° C. or more for 1 hour or more under reducedpressure. It is more preferable to carry out drying at 60 to 200° C. forone to 24 hours, and most preferable at 80 to 160° C. for 4 to 18 hours.

Specific example of the production process of the compound representedby the general formula [8] is further shown below in detail when M⁴ is azinc atom and the treating agent is a phenol, include the followingsteps: hexane is used as a solvent; a hexane solution of a dialkylzinc(for example, diethylzinc) is added thereto and cooled at −78° C.; ahydrocarbon solution of the phenol which are 2-fold molar amount to thedialkylzinc is added dropwise; and the resulting mixture is stirred atroom temperature for 10 minutes to 24 hours. Of course, those used inthese treatments are not limited to the dialkylzinc and phenol.

Then, the compound [E] represented by the above-mentioned generalformula [9] is illustrated.

M⁵ has been already illustrated.

X² in the general formula [9] is the same as X¹ in the general formula[8] which has been already illustrated, and preferable elements are alsothe same as in X¹.

Further, “u” in the above-mentioned general formula [9] represents avalence of X², when X² is an atom of the Group XIV, “u” is 4, when X² isan atom of the Group XV, “u” is 3, and when X² is an atom of Group XVI,“u” is 2.

R⁹ in the general formula [9] represents an electron-withdrawing groupor a group containing an electron-withdrawing group, and when a pluralnumber of R⁹'s exist, they may be mutually the same or different. Theexemplification of the electron-withdrawing group or the groupcontaining an electron-withdrawing group is selected from those alreadydescribed in the illustration of R¹ and R³, and the preferable group isthe same group as in R¹ and R³. Specific example of X²R⁹ _(u-1) which isa combination of X² and R⁹ and preferable specific example thereof arethe same as the specific example X¹R⁷i which is previously illustratedwhen X² is a carbon atom, a nitrogen atom or an oxygen atom.

R¹⁰ in the general formula [9] represents a hydrogen atom, a halogenatom or a hydrocarbon group, and when a plural number of R¹⁰'s exist,they may be mutually the same or different.

Specific example and preferable specific example of R¹⁰ are also thesame as in R⁸ in the general formula [8] which is previously described.

T⁴ in the general formula [9] represents an atom of Group XIII of thePeriodic Table. Specific examples thereof include a boron atom, analuminum atom, a gallium atom and the like, and in particular, a boronatom is preferable. “m” in the general formula [9] represents a numeralsatisfying 1≦m≦3, and “m” is preferably 2. Two or more of molecules ofthe compound represented by the general formula [9] may be associated.

Among the compound represented by the general formula [9], specificexamples of a case in which M⁵ is a zinc atom includebis(fluoroalkyloxyzincoxy)alkylborane such asbis(trifluoromethoxyzincoxy)methylborane,bis(1,1,3,3,3-pentafluoro-2-trifluoromethylpropoxyzincoxy)methylboraneand bis(2,2,2-trifluoro-1-trifluoromethylmethoxyzincoxy)methylborane;bis(fluoroalkyloxyzincoxy)alkylborane such asbis(2,2,2-trifluoroethoxyzincoxy)methylborane andbis(2,2,3,3,3-pentafluoropropoxyzincoxy)methylborane;bis(fluoroaryloxyzincoxy)alkylborane such asbis(2,4,6-trifluorophenoxyzincoxy)methylborane,bis(3,4,5-trifluorophenoxyzincoxy)methylborane andbis(pentafluorophenoxyzincoxy)methylborane; andbis(4-trifluoromethylphenoxyzincoxy)methylborane,bis(trifluoromethylamidozincoxy)methylborane,bis(2,2,2-trifluoroethylamidozincoxy)methylborane,bis(pentafluoroanilidozincoxy)methylborane,bis(N-trifluoromethylanilidozincoxy)methylborane and the like.

In particular, the compound represented by the general formula [9] ispreferably a bis(fluoroalkyloxyzincoxy)alkylborane or abis(fluoroaryloxyzincoxy)alkylborane, and further preferablybis(2,2,2-trifluoro-1-trifluoromethylethoxyzincoxy)methylborane,bis(3,4,5-trifluorophenoxyzincoxy)methylborane,bis(pentafluorophenoxyzincoxy)methylborane orbis(1,1,3,3,3-pentafluoro-2-trifluoromethylpropoxyzincoxy)methylborane.

The production process of the compound represented by the generalformula [9] is not specifically limited, and for example, a process oftreating the organometallic compound such as an alkylmetal, ahalogenated alkylmetal or the like with an inorganic acid such as analkylboric acid or the like, and thereafter, with the compoundrepresented by LiX²R⁹ _(u-1) such as an alkyloxylithium compound,aryloxylithium compound or aminolithium compound having anelectron-withdrawing substituent, or the compound represented by HX²R⁹_(u-1) such as an alcohol, phenol or amine having anelectron-withdrawing substituent or the like, is mentioned. A process oftreating the organometallic compound such as an alkylmetal, ahalogenated alkylmetal or the like with the compound selected from analcohol, phenol or amine having an electron-withdrawing substituent, ispreferable.

The treatment is preferably carried out under inert gas atmosphere. Thetreatment temperature is usually from −100° C. to 200° C., andpreferably from −80° C. to 150° C. The treatment time is usually from 1minute to 36 hours, and preferably from 10 minutes to 24 hours. Further,the treatment may use a solvent, and these compounds may be directlytreated without using it. The solvent used is preferably an aliphatichydrocarbon solvent, an aromatic hydrocarbon solvent or an ether-basedcompound which is inert to the organometallic compound, the compoundrepresented by LiX²R⁹ _(u-1), the compound represented by HX²R⁹ _(u-1)and the like. Specific examples of the solvent is the same examplesspecifically mentioned in the item of the compound [A].

Further, in the treatment, the order of dropwise addition of theorganometallic compound, the compound represented by LiX²R⁹ _(u-1) andthe compound represented by HX²R⁹ _(u-1) is not specifically limited, itmay be successively dropwise added, may be simultaneously dropwiseadded, and 2 or more of solvents may be dropwise added after mixing.Arbitrary amounts of (X²R⁹ _(u-1)) and R¹⁰ can be introduced byadjusting the molar number of the compound represented by LiX²R⁹ _(u-1)and the compound represented by HX²R⁹ _(u-1) to the organometalliccompound. Further, as a result of the treatment, the organometalliccompound being a raw material, the compound represented by LiX²R⁹_(u-1), the compound represented by HX²R⁹ _(u-1) and the like may remainas unreacted matters. The compound represented by the general formula[9] which was obtained by the treatment can be used as a catalystcomponent for addition polymerization after carrying out separation andpurification such as recrystallization or the like, but the reactedsolution can be also used as a catalyst component for additionpolymerization. The solvent is preferably removed by distillation fromthe reacted solution, and drying is preferably carried out at atemperature of 25° C. or more for 1 hour or more under reduced pressure.It is more preferable to carry out drying at 60 to 200° C. for one to 24hours, and most preferable at 80 to 160° C. for 4 to 18 hours.

Specific example of the production process of the compound representedby the general formula [9] is further shown below in detail when M⁵ is azinc atom, an inorganic acid is an alkylboric acid and the treatingagent is a phenol. A process that a toluene slurry of the alkylboricacid is cooled to −78° C., a prescribed amount of a hexane solution of adialkylzinc is added dropwise while vigorously stirring the slurry, thetemperature of the mixture is gradually raised to room temperature aftercompletion of dropwise addition, further stirring is carried out for afixed time, a prescribed amount of phenols is gradually added dropwise,and further stirring is carried out for a fixed time, can be adopted.

Of course, compounds used in these treatments are not limited to thealkylboric acid, the dialkylzinc and the phenol.

The compounds [A] to [E] which are described above in detail are usefulas the catalyst component for addition polymerization (particularly,catalyst component for olefin polymerization). Specific examples of thecatalyst for addition polymerization of the present invention include acatalyst for addition polymerization obtained by contacting the compound(I) selected from the above-mentioned compounds [A] to [E] as a catalystcomponent for addition polymerization with the compound with a metalcompound (II) of the Group III to the Group XII or lanthanide series,and a catalyst for addition polymerization obtained by contacting thecatalyst component for addition polymerization (I), a metal compound(II) of the Group III to the Group XII or lanthanide series, and anorganoaluminum compound (III).

Next, a catalyst for addition polymerization is described in detailbelow.

(II) Metal compound of the Groups III to XIII or Lanthanide Series

As the metal compound (II)of the Groups III to XII or Lanthanide Seriesused for addition polymerization catalyst of the present invention, ametal compound which is different from the above-described compound(I)is used, and it is not specifically limited so far as it is a metalcompound of the Groups III to XIII or Lanthanide Series of the PeriodicTable exhibiting an addition polymerization activity by using togetherwith the compound(I), or compound(I) and an organoaluminum compound, asan activating co-catalyst component. Examples of the metal compound(II)includes metal compounds indicated by the general formula [10] describedbelow, μ-oxo type metal compounds and the like.

L_(a)MX_(b)  [10]

(wherein M is a metal atom of the Group 3 to Group 13 or LanthanideSeries of the Periodic Table of the Elements; L is a group having acyclopentadienyl type anion skeleton or a group containing ahetero-atom, a plurality of L groups may be the same or different, and aplurality of L groups may be optionally linked in direct, or through agroup containing a carbon atom, a silicone atom, a nitrogen atom, anoxygen atom, a sulfur atom or a phosphorus atom; X is a halogen atom ora hydrocarbon group having 1 to 20 carbon atoms; a represents a numeralsatisfying an expression of 0<a≦8; b represents a numeral satisfying anexpression of 0<b≦8.)

In the general formula [10] representing the metal compound, M is ametal atom of the Group 3 to Group 13 of the Periodic Table (IUPAC 1985)or Lanthanide Series. Specific examples of the metal atom include ascandium atom, yttrium atom, titanium atom, zirconium atom, hafniumatom, vanadium atom, niobium atom, tantalum atom, chromium atom, ironatom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladiumatom, samarium atom, ytterbium atom, aluminum atom, boron atom and thelike.

As the metal compound, M is preferably a transition metal compound, morepreferably a titanium atom, zirconium atom or hafnium atom.

In the general formula [10], L is a group having a cyclopentadienyl typeanion skeleton or a group containing a hetero-atom, and a plurality of Lgroups may be the same or different. Further, L groups may be optionallylinked in direct, or through a group containing a carbon atom, asilicone atom, a nitrogen atom, an oxygen atom, a sulfur atom or aphosphorus atom.

A cyclopentadienyl type anion skeleton in L includes a cyclopentadienylgroup, a substituted cyclopentadienyl group, an indenyl group, asubstituted -indenyl group, a fluorenyl group, a substituted fluorenylgroup and the like. Examples of the group having a cyclopentadiene typeanion skeleton include an η⁵-(substituted)cyclopentadienyl group, anη⁵-(substituted)indenyl group, an η⁵-(substituted) fluorenyl group andthe like. Specific examples include an η⁵-cyclopentadienyl group, anη⁵-methylcyclopentadienyl group, an η⁵-tert-butylcyclopentadienyl group,an η⁵-1,2-dimethylcyclopentadienyl group, anη⁵-1,3-dimethylcyclopentadienyl group, anη⁵-1-tert-butyl-2-methylcyclopentadienyl group, anη⁵-1-tert-butyl-3-methylcyclopentadienyl group, anη⁵-1-methyl-2-isopropylcyclopentadienyl group, anη⁵-1-methyl-3-isopropylcyclopentadienyl group, anη⁵-1,2,3-trimethylcyclopentadienyl group, anη⁵-1,2,4-trimethylcyclopentadienyl group, anη⁵-tetramethylcyclopentadienyl group, an η⁵-pentamethylcyclopentadienylgroup, an η⁵-indenyl group, an η⁵-4,5,6,7-tetrahydroindenyl group, anη⁵-2-methylindenyl group, an η⁵-3-methylindenyl group, anη⁵-4-methylindenyl group, an η⁵-5-methylindenyl group, anη⁵-6-methylindenyl group, an η⁵-7-methylindenyl group, anη⁵-2-tert-butylindenyl group, an η⁵-3-tert-butylindenyl group, anη⁵-4-tert-butylindenyl group, an η⁵-5-tert-butylindenyl group, anη⁵-6-tert-butylindenyl group, an η⁵-7-tert-butylindenyl group, anη⁵-2,3-dimethylindenyl group, an η⁵-4,7-dimethylindenyl group, anη⁵-2,4,7-trimethylindenyl group, an η⁵-2-methyl-4-isopropylindenylgroup, an η⁵-4,5-benzindenyl group, an η⁵-2-methyl-4,5-benzindenylgroup, an η⁵-4-phenylindenyl group, an η⁵-2-methyl-5-phenylindenylgroup, an η⁵-2-methyl-4-phenylindenyl group, anη⁵-2-methyl-4-naphthylindenyl group, an η⁵-fluorenyl group, anη⁵-2,7-dimethylfluorenyl group, an η⁵-2,7-di-tert-butylfluorenylgroup(herein-after, η⁵ may be omitted for simplifying), and substitutionproducts thereof, etc.

The hetero-atom in the group containing a hetero-atom includes an oxygenatom, a sulfur atom, a nitrogen atom, a phosphorus atom and the like,and examples thereof include an alkoxy group, an aryloxy group, athioalkoxy group, a thioaryloxy group, an alkylamino group, an arylaminogroup, an alkylphosphino group, an arylphosphino group, or an aromaticor aliphatic heterocyclic group having an oxygen atom, a sulfur atom, anitrogen atom and/or a phosphorus atom within the ring, and a chelatingligand.

Specific examples of the group containing a hetero-atom include amethoxy group, an ethoxy group, a n- or iso-propoxy group, a n-, sec-,iso- or tert-butoxy group, a phenoxy group, a 2-methylphenoxy group, a2,6-dimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a2-ethylphenoxy group, a 4-n-propylphenoxy group, a 2-isopropylphenoxygroup, a 2,6-diisopropylphenoxy group, a 4-sec-butylphenoxy group, a4-tert-butylphenoxy group, a 2,6-di-sec-butylphenoxy group, a4-tert-butyl-4-methylphenoxy group, a 2,6-di-tert-butylphenoxy group, a4-methoxyphenoxy group, a 2,6-dimethoxyphenoxy group, a3,5-dimethoxyphenoxy group, a 2-chlorophenoxy group, a 4-nitrosophenoxygroup, a 4-nitrophenoxy group, a 2-aminophenoxy group, a 3-aminophenoxygroup, a 4-aminothiophenoxy group, a 2,3,6-trichlorophenoxy group, a2,4,6-trifluorophenoxy group, a thiomethoxy group, a dimethylaminogroup, a diethylamino group, a di-n- or iso-propylamino group, adiphenylamino group, an isopropylamino group, a tert-butylamino group, apyrrolyl group, a dimethylphosphino group, a 2-(2-oxy-1-propyl)phenoxygroup, catechol, resorcinol, 4-isopropylcatechol, 3-methoxycatechol, a1,8-dihydroxynahpthyl group, a 1,2-dihydroxynahpthyl group, a2,2′-biphenyldiol group, a 1,1′-bi-2-naphthol group, a2,2′-dihydroxy-6,6′-dimethylbiphenyl group, a4,4′,6,6′-tetra-tert-butyl-2,2′-methylenediphenoxy group, a4,4′,6,6′-tetramethyl-2,2′-isobutylidenediphenoxy group and the like.

Further, the hetero atom-containing group includes a group representedby the formula [11]:

R^(a) ₃P═N—

(wherein R^(a) represents a hydrogen atom, halogen atom or hydrocarbongroup, R^(a) groups may be the same or different, and two of them may bebonded mutually and may form a ring.)

Specific Examples of R^(a) include a hydrogen atom, fluorine atom,chlorine atom, bromine atom, iodine atom, methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, tert-butyl group,cyclohexyl group, phenyl group, 1-naphtyl group, benzyl group and thelike, but are not limited thereto.

Further, the hetero atom-containing group also includes a grouprepresented by the general formula [12]:

(wherein respective R^(b) groups independently represent a hydrogenatom, halogen atom, hydrocarbon group, halogenated hydrocarbon group,hydrocarbon oxy group, silyl group or amino group, they may be the sameor different, and two or more of them may be bonded mutually and mayform a ring.)

Specific Examples of R^(b) in the general formula [12] include ahydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom,phenyl group, 1-naphtyl group, 2-naphtyl group, tert-butyl group,2,6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group,4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group,cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group,triethylsilyl group, diphenylmethylsilyl group, 1-methy-1-phenylethylgroup, 1,1-dimethyl propyl group, 2-chlorophenyl group and the like, butare not limited thereto.

Further, the chelating ligand means a ligand having a plural number ofcoordinating positions, and specific examples thereof include anacetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine,acylhydrazone, diethylenetriamine, triethylenetetramine, porphyrin,crown ether, cryptate and the like.

The mutual groups having the cyclopentadienyl type anion skeleton, thegroup having a cyclopentadienyl type anion skeleton and the groupcontaining a hetero-atom, or the mutual groups containing a hetero-atommay be directly linked, or may be linked through a group containing acarbon atom, a silicone atom, a nitrogen atom, an oxygen atom, a sulfuratom or a phosphorus atom, respectively. Examples of the group includealkylene groups such as an ethylene group, a propylene group and thelike, substituted alkylene groups such as a dimethylmethylene group, adiphenylmethylene group and the like, or a silylene group, substitutedsilylene groups such as a dimethylsilylene group, a diphenylsilylenegroup, a tetramethyldisilylene group and the like, or hetero-atoms suchas a nitrogen atom, an oxygen atom, a sulfur atom and/or a phosphorusatom and the like, etc.

X in the general formula [10] representing the transition metal compoundis a halogen atom or a hydrocarbon group having 1 to 24 carbon atoms.Specific examples of X include a halogen atom such as a fluorine atom,chlorine atom, bromine atom, and iodine atom and hydrocarbon grouphaving 1 to 24 carbon atoms such as a methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, phenyl group, benzylgroup and the like, and preferably include a halogen atom, alkyl grouphaving 1 to 24 carbon atoms and aralkyl group having 7 to 24 carbonatoms.

In the general formula [10], “a” represents a numeral satisfying anexpression of 0<a≦8, “b” represents a numeral satisfying an expressionof 0<b≦8, and “a” and “b” are properly selected depending on the valencyof M.

Among the metal compounds(II), specific examples of the compound inwhich a metal atom is a titanium atom includebis(cyclopentadienyl)titanium dichloride,bis(methylcyclopentadienyl)titanium dichloride,bis(n-butylcyclopentadienyl)titanium dichloride,bis(dimethylcyclopentadienyl)titanium dichloride,bis(ethylmethylcyclopentadienyl)titanium dichloride,bis(trimethylcyclopentadienyl)titanium dichloride,bis(tetramethylcyclopentadienyl)titanium dichloride,bis(pentamethylcyclopentadienyl)titanium dichloride,bis(indenyl)titanium dichloride, bis(4,5,6,7-tetrahydroindenyl)titaniumdichloride, bis(fluorenyl)titanium dichloride,cyclopentadienyl(pentamethylcyclopentadienyl) titanium dichloride,cyclopentadienyl(indenyl) titanium dichloride,cyclopentadienyl(fluorenyl) titanium dichloride,indenyl(fluorenyl)titanium dichloride, pentamethylcyclopentadienyl(indenyl)titanium dichloride,pentamethylcyclopentadienyl(fluorenyl)titanium dichloride,ethylenebis(cyclopentadienyl)titanium dichloride,ethylenebis(2-methylcyclopentadienyl)titanium dichloride,ethylenebis(3-methylcyclopentadienyl)titanium dichloride,ethylenebis(2-n-butylcyclopentadienyl)titanium dichloride,ethylenebis(3-n-butylcyclopentadienyl)titanium dichloride,ethylenebis(2,3-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,4-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,5-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(3,4-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,3-ethylmethylcyclopentadienyl)titanium dichloride,ethylenebis(2,4-ethylmethylcyclopentadienyl)titanium dichloride,ethylenebis(2,5-ethylmethylcyclopentadienyl)titanium dichloride,ethylenebis(3,5-ethylmethylcyclopentadienyl)titanium dichloride,ethylenebis(2,3,4-trimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,3,5-trimethylcyclopentadienyl)titanium dichloride,ethylenebis(tetramethylcyclopentadienyl) titanium dichloride,ethylenebis(indenyl)titanium dichloride,ethylenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride,ethylenebis(2-phenylindenyl)titanium dichloride,ethylenebis(2-methylindenyl)titanium dichloride,ethylenebis(2-methyl-4-phenylindenyl)titanium dichloride,ethylenebis(2-methyl-4-naphthylindenyl)titanium dichloride,ethylenebis(2-methyl-4,5-benzoindenyl)titanium dichloride,ethylenebis(fluorenyl)titanium dichloride, ethylene(cyclopentadienyl)(pentamethylcyclopentadienyl)titanium dichloride,ethylene(cyclopentadienyl)(indenyl)titanium dichloride,ethylene(methylcyclopentadienyl) (indenyl)titanium dichloride,ethylene(n-butylcyclopentadienyl)(indenyl)titanium dichloride,ethylene(tetramethylcyclopentadienyl) (indenyl)titanium dichloride,ethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,ethylene(methylcyclopentadienyl) (fluorenyl)titanium dichloride,ethylene (pentamethylcyclopentadienyl)(fluorenyl)titanium dichloride,ethylene(n-butylcyclopentadienyl) (fluorenyl)titanium dichloride,ethylene (tetramethylpentadienyl)(fluorenyl)titanium dichloride,ethylene(indenyl)(fluorenyl)titanium dichloride,isopropylidenebis(cyclopentadienyl) titanium dichloride,isopropylidenebis(2-methylcyclopentadienyl)titanium dichloride,isopropylidenebis(3-methylcyclopentadienyl)titanium dichloride,isopropylidenebis(2-n-butylcyclopentadienyl)titanium dichloride,isopropylidenebis(3-n-butylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,4-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,5-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(3,4-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3-ethylmethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,4-ethylmethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,5-ethylmethylcyclopentadienyl)titanium dichloride,isopropylidenebis(3,5-ethylmethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3,4-trimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3,5-trimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(tetramethylcyclopentadienyl)-titanium dichloride,isopropylidenebis(indenyl) titanium dichloride,isopropylidenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride,isopropylidenebis(2-phenylindenyl)titanium dichloride,isopropylidenebis(2-methylindenyl)titanium dichloride,isopropylidenebis(2-methyl-4-phenylindenyl)titanium dichloride,isopropylidenebis(2-methyl-4-naphthylindenyl)titanium dichloride,isopropylidenebis(2-methyl-4,5-benzoindenyl)titanium dichloride,isopropylidenebis(fluorenyl)titanium dichloride,isopropylidene(cyclopentadienyl) (tetramethylcyclopentadienyl)titaniumdichloride, isopropylidene(cyclopentadienyl)(indenyl)titaniumdichloride, isopropylidene(methylcyclopentadienyl) (indenyl)titaniumdichloride, isopropylidene(n-butylcyclopentadienyl)(indenyl)titaniumdichloride, isopropylidene(tetramethylcyclopentadienyl)(indenyl)titanium dichloride, isopropylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,isopropylidene(methylcyclopentadienyl)(fluorenyl)titanim dichloride,isopropylidene(n-butylcyclopentadienyl) (fluorenyl) titanium dichloride,isopropylidene (tetramethylcyclopentadienyl) (fluorenyl)titaniumdichloride, isopropylidene (indenyl)(fluorenyl)titanium dichloride,

dimethylsilylenebis(cyclopentadienyl)titanium dichloride,dimethylsilylenebis(2-methylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(3-methylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2-n-butylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(3-n-butylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,3-dimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,4-dimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,5-dimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(3,4-dimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,3-ethylmethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,4-ethylmethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,5-ethylmethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(3,5-ethylmethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,3,4-trimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(tetramethylcyclopentadienyl)-titanium dichloride,dimethylsilylenebis(indenyl)titanium dichloride,dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride,dimethylsilylenebis(2-methylindenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4-phenylindenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4-naphthylindenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4,5-benzoindenyl)titanium dichloride,dimethylsilylene(cyclopentadienyl)(indenyl)titanium dichloride,dimethylsilylene(methylcyclopentadienyl) (indenyl)titanium dichloride,dimethylsilylene(n-butylcyclopentadienyl)(indenyl)titanium dichloride,dimethylsilylene(tetramethylcyclopentadienyl) (indenyl)titaniumdichloride, dimethylsilylene (cyclopentadienyl)(fluorenyl)titaniumdichloride, dimethylsilylene(methylcyclopentadienyl)(fluorenyl) titaniumdichloride, dimethylsilylene(n-butylcyclopentadienyl) (fluorenyl)titanium dichloride, dimethylsilylene-(tetramethylcyclopentadienyl)(indenyl)titanium dichloride,dimethylsilylene-(indenyl)(fluorenyl)titanium dichloride,

cyclopentadienyltitanium trichloride,pentamethylcyclopentadienyltitanium trichloride,cyclopentadienyl(dimethylamido)titanium dichloride,cyclopentadienyl(phenoxy)titanium dichloride,cyclopentadienyl(2,6-dimethylphenyl)titanium dichoride, cyclopentadienyl(2,6-d-isopropylphenyl)titanium dichloride,cyclopentadienyl(2,6-di-tert-butylphenyl)titanium dichloride,pentamethylcyclopentadienyl(2,6-dimethylphenyl)titanium dichloride,pentamethylcyclopentadienyl(2,6-disopropylphenyl)titanium dichloride,pentamethylcyclopentadienyl(2,6-di-tert-butylphenyl)titanium dichloride,indenyl(2,6-diisopropylphenyl)titanium dichloride,fluorenyl-(2,6-diisopropylphenyl)titanium dichloride,methylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,methylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride,methylene(tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,methylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

methylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,methylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,methylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride,methylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,isopropylidene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3-phenyl-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride,isopropylidene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-methoxy-2phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilylene(cyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene-(cyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(2-phenoxy)titanium-dichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,di-methylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilylene(indenyl)(2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-methyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloridedimethylsilylene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilylene(indenyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilylene(fluorenyl)(2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-methyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilylene(fluorenyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(1-naphthox-2-yl)titaniumdichloride and the like, and compounds wherein (2-phenoxy) of thesecompounds is replaces with (3-phenyl-2-phenoxy),(3-trimethylsilyl-2-phenoxy) or (3-tert-butyldimethylsilyl-2-phenoxy),compounds wherein dimethylsilylene of these compounds is replaced withdiethylsilylene, diphenylsilylene or dimethoxysilylene, compoundswherein dichloride of these compounds is replaced with difluoride,dibromide, diiodide, dimethyl, diethyl, diisopropyl, bis(dimethylamido),bis(diethylamido), dimethoxide, diethoxide, di-n-butoxide ordiisopropoxide.(tert-butylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdichloride,(tert-butylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdimethyl,(tert-butylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdibenzyl,(methylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdichloride,(ethylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdichloride, (tert-butylamido)tetramethylcyclopentadienyldimethylsilanetitanium dichloride,(tert-butylamido)tetramethylcyclopentadienyldimethylsilane titaniumdimethyl, (tert-butylamido)tetramethylcyclopentadienyldimethylsilane-titanium dibenzyl,(benzylamido)tetramethylcyclopentadienyl-dimethylsilanetitaniumdichloride, (phenylphosphido)tetramethylcyclopentadienyldimethyl-silanetitanium dibenzyl,(tert-butylamido)indenyl-1,2-ethanedlyltitanium dichloride,(tert-butylamido)indenyl-1,2-ethanediyltitanium dimethyl,(tert-butylamido)tetrahydroindenyl-1,2-ethanediyltitanium dichloride,(tert-butylamido)tetrahydroindenyl-1,2-ethanediyltitanium dimethyl,(tert-butylamido)fluorenyl-1,2-ethanediyltitanium dichloride,(tert-butylamido)fluorenyl-1,2-ethanediyltitanium dimethyl,(tert-butylamido)indenyldimethylsilanetitanium dichloride,(tert-butylamido)indenyldimethylsilanetitaniumdimethyl,(tert-butylamido)tetrahydroindenyldimethylsilanetitaniumdichloride, (tert-butylamido)tetrahydroindenyldimethylsilanetitaniumdimethyl, (tert-butylamido)fluorenyldimethylsilanetitanium dichloride,(tert-butylamido)fluorenyldimethylsilanetitanium dimethyl,(dimethylaminomethyl)tetramethylcyclopentadienyl-titanium(III)dichloride,(dimethylaminoethyl)tetramethylcyclopentadienyl-titanium(III)dichloride,(dimethylaminopropyl)tetramethylcyclopentadienyl-titanium(III)dichloride, (N-pyrrolidinylethyl)tetramethylcyclopentadienyl-titaniumdichloride, (B-dimethylaminoborabenzene)cyclopentadienylzirconiumdichloride, cyclopentadienyl(9-mesitylboraanthracenyl)zirconiumdichloride, 2,2′-thiobis[4-methyl-6-(1-methylethyl)phenoxy]titaniumdichloride, 2,2′-thiobis(4,6-dimethylphenoxyltitanium dichloride,2,2′-thiobis(4-methyl-6-tert-butylphenoxy)titanium dichloride,2,2′-methylenebis(4-methyl-6-tert-butylphenoxy)titanium dichloride,2,2′-ethylenebis(4-methyl-6-tert-butylphenoxy)titanium dichloride,2,2′-sulfinylbis(4-methyl-6-tert-butylphenoxy)titanium dichloride,2,2′-(4,4′,6,6′-tetra-tert-butyl-1,1′-biphenoxy)titanium dichloride,2,2′-thiobis[4-methyl-6-tert-butylphenoxy]titanium diisopropoxide,2,2′-methylenebis(4-methyl-6-tert-butylphenoxy)titanium diisopropoxide,2,2′-ethylenebis(4-methyl-6-tert-butylphenoxy)titanium diisopropoxide,2,2′-sulfinylbis(4-methyl-6-tert-butylphenoxy)titanium diisopropoxide,(di-tert-butyl-1,3-propanediamido)titanium dichloride,(dicyclohexyl-1,3-propanediamido) titanium dichloride,[bis(trimethylsilyl)-1,3-propanediamido]titanium dichloride,[bis(tert-butyldimethylsilyl)-1,3-propanediamido]titanium dichloride,[bis(2,6-dimethylphenyl)-1,3-propanediamido]titanium dichloride,[bis(2,6-diisopropylphenyl)-1,3-propanediamido]titanium dichloride,[bis(2,6-di-tert-butylphenyl)-1,3-propanediamido]titanium dichloride,[bis(triisopropylsilyl)naphthalenediamido]titanium dichloride,[bis(trimethylsilyl)naphthalenediamido]titanium

dichloride, [bis(tert-butyldimethylsilyl)naphthalenediamido]titaniumdichloride, [bis(tert-butyldimethylsilyl)naphthalenediamido]titaniumdibromide, [hydrotris(3,5-dimethylpyrazolyl)borate]titanium trichloride,[hydrotris(3,5-dimethylpyrazolyl)borate]titanium tribromide,[hydrotris(3,5-dimethylpyrazolyl)borate]titanium triiodide,[hydrotris(3,5-diethylpyrazolyl)borate]titanium trichloride,[hydrotris(3,5-diethylpyrazolyl)borate]titanium tribromide,[hydrotris(3,5-diethylpyrazolyl)borate]titanium triiodide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]titanium trichloride,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]titanium tribromide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]titanium triiodide,[tris(3,5-dimethylpyrazolyl)methyl]titanium trichloride,[tris(3,5-dimethylpyrazolyl)methyl]titanium tribromide,[tris(3,5-dimethylpyrazolyl)methyl]titanium triiodide,[tris(3,5-diethylpyrazolyl)methyl]titanium trichloride,[tris(3,5-diethylpyrazolyl)methyl]titanium tribromide, [tris(3,5-diethylpyrazolyl)methyl]titanium triiodide,[tris(3,5-di-tert-butylpyrazolyl)methyl]titanium trichloride,[tris(3,5-di-tert-butylpyrazolyl)methyl]titanium tribromide,[tris(3,5-di-tert-butylpyrazolyl)methyl]titanium triiodide and the like,compounds in which titanium of these compounds is replaced withzirconium or hafnium, compounds in which (2-phenoxy) of these compoundsis replaced with (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy) or(3-tert-butyldimethylsilyl-2-phenoxy), compounds in whichdimethylsilylene of these compounds is replaced with diethylsilylene,diphenylsilylene, or dimethoxysilylene, compounds in which dichloride ofthese compounds is replaced with difluoride, dibromide, diiodide,dimethyl, diethyl, diisopropyl, bis(dimethylamide), bis(diethylamide),dimethoxide, diethoxide, di-n-butoxide, diisopropoxide or bis(diacetoxy)and the like.

Among the metal compounds(II) represented by the general formula [10],specific examples of a compound in which a metal atom is a nickel atominclude 2,2′-methylenebis[(4R)-4-phenyl-5,5′-dimethyloxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-dimethyloxazoline]nickel dibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diethyloxazoline]nickel dichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diethyloxazoline]nickel dibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5!-di-n-propyloxazoline]nickeldichloride,2,2!-methyleneb[(4R)-4-phenyl-5,51-di-n-propyloxazoline]nickeldibromide, 2,2!-methyleneb[(4R)-4-phenyl-5,5′-disopropyloxazoline]nickel dichloride,2,2′-methyleneb[(4R)-4-phenyl-5,5′-diisopropyloxazoline]nickeldibromide,2,2′-methyleneb[(4R)-4-phenyl-5,5′-dicyclohexyloxazoline]nickeldichloride,2,2′-methyleneb[(4R)-4-phenyl-5,5′-dicyclohexyloxazoline]nickeldibromide, 2,2′-methyleneb[(4R)-4-phenyl-5,5′-dimethoxyoxazoline]nickeldichloride, 2,2′-methyleneb[(4R)-4-phenyl-5,5′-dimethoxyoxazoline]nickeldibromide, 2,2′-methyleneb[(4R)-4-phenyl-5,5′-diethoxyoxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diethoxyoxazoline]nickel dibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diphenyloxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diphenyloxazoline]nickel dibromide,methylenebis[(4R)-4-methyl-5,5′-di-(2-methylphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(3-methylphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(4-methylphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(2-methoxyphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(3-methoxyphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(4-methoxyphenyl)oxazoline]nickeldibromide,methylenebis[spiro{(4R)-4-methyloxazoline-5,1′-cyclobutane}]nickeldibromide,methylenebis[spiro{(4R)-4-methyloxazoline-5,1′-cyclopentane}]nickeldibromide,methylenebis[spiro{(4R)-4-methyloxazoline-5,1′-cyclohexane}]nickeldibromide,methylenebis[spiro{(4R)-4-methyloxazoline-5,1′-cycloheptane}]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-dimethyloxazoline]nickeldibromide,2,21-methylenebis[(4R)-4-isopropyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-n-propyloxazoline]nickeldibromide, methylenebis[(4R)-4-isopropyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-dicyclohexyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-diphenyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isopropyloxazoline-5,1′-cyclobutane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isopropyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isopropyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isopropyloxazoline-5,1′-cycloheptane}]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-dimethyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-isobutyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-dicyclohexyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-diphenyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isobutyloxazoline-5,1′-cyclobutanel}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isobutyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isobutyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isobutyloxazoline-5,1′-cycloheptane}]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-dimethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-diphenyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-dicyclohexyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,21-methylenebis[(4R)-4-tert-butyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-tert-butyloxazoline-5,1′-cyclobutane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-tert-butyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-tert-butyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-tert-butyloxazoline-5,1′-cycloheptane}]nickeldibromide, 2,2′-methylenebis[(4R)-4-phenyl-5,5-dimethyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-phenyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-dicyclohexyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-phenyl-5,5-diphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,21-methylenebis[(4R)-4-phenyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,methylenebis[spiro{(4R)-4-phenyloxazoline-5,1′-cyclobutane)}nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-phenyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-phenyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-phenyloxazoline-5,1′-cycloheptane}]nickeldibromide, 2,2′-methylenebis[(4R)-4-benzyl-5,5-dimethyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-benzyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-dicyclohexyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-benzyl-5,5-diphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,21-methylenebis[(4R)-4-benzyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2-methylenebis[(4R)-4-benzyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-benzyloxazoline-5,1′-cyclobutane}] nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-benzyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-benzyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-benzyloxazoline-5,1′-cycloheptane}]nickeldibromide, and compounds in which (4R) in each of the above-mentionedcompounds corresponds to (4S), etc. Further, examples of the meso typeisomer include compounds in which (4R) of two skeletons in each of thecompounds which are mentioned above as the optically active substancesof bisoxazolines were changed to (4R) of one oxazoline skeleton and (4S)of another oxazoline skeleton, and[hydrotris(3,5-dimethylpyrazolyl)borate]nickel chloride,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel bromide,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel iodide,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel methyl,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel ethyl, [hydrotris(3,5-dimethylpyrazolyl) borate] nickel allyl,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel methallyl,(hydrotris(3,5-diethylpyrazolyl)borate]nickel chloride,[hydrotris(3,5-diethylpyrazolyl)borate]nickel bromide,[hydrotris(3,5-diethylpyrazolyl)borate]nickel iodide,[hydrotris(3,5-diethylpyrazolyl)borate]nickel methyl,[hydrotris(3,5-diethylpyrazolyl)borate]nickel ethyl,[hydrotris(3,5-diethylpyrazolyl)borate]nickel allyl,[hydrotris(3,5-diethylpyrazolyl)borate]nickel methallyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel chloride,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel bromide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel iodide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel methyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel ethyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel allyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel methallyl, compoundsindicated by the structural formula described below:

(wherein each of R^(c) and R^(d) is a 2,6-diisopropylphenyl group, andX, R^(e) and R^(f) are any one of the combination of the substituentsrepresented in Table 1 described below.) R⁹ and R¹⁰ may be one bi-valentgroup (e.g. a acenaphthyl group) in one united body.

TABLE 1 R^(e) = R^(f) = H R^(e) = R^(f) = methyl Acenaphthyl by R^(e) &R^(f) X^(a) = F X^(a) = F X^(a) = F R^(e) = R^(f) = H R^(e) = R^(f) =methyl Acenaphthyl by R^(e) & R^(f) X^(a) = Cl X^(a) = Cl X^(a) = ClR^(e) = R^(f) = H R^(e) = R^(f) = methyl Acenaphthyl by R^(e) & R^(f)X^(a) = I X^(a) = I X^(a) = I R^(e) = R^(f) = H R^(e) = R^(f) = methylAcenaphthyl by R^(e) & R^(f) X^(a) = Methyl X^(a) = methyl X^(a) =methyl R^(e) = R^(f) = H R^(e) = R^(f) = methyl Acenaphthyl by R^(e) &R^(f) X^(a) = Ethyl X^(a) = ethyl X^(a) = ethyl R^(e) = R^(f) = H R^(e)= R^(f) = methyl Acenaphthyl by R^(e) & R^(f) X^(e) = n-propyl X^(a) =n-propyl X^(a) = n-propyl R^(e) = R^(f) = H R^(e) = R^(f) = methylAcenaphthyl by R^(e) & R^(f) X^(a) = isopropyl X^(a) = isopropyl X^(a) =isopropyl R^(e) = R^(f) = H R^(e) = R^(f) = methyl Acenaphthyl by R^(e)& R^(f) X^(a) = n-butyl X^(a) = n-butyl X^(a) = n-butyl R^(e) = R^(f) =H R^(e) = R^(f) = methyl Acenaphthyl by R^(e) & R^(f) X^(a) = phenylX^(a) = phenyl X^(a) = phenyl R^(e) = R^(f) = H R^(e) = R^(f) = methylAcenaphthyl by R^(e) & R^(f) X^(a) = benzyl X^(a) = benzyl X^(a) =benzyl

Further, compounds wherein a nickel atom is replaced with a palladiumatom, a cobalt atom, a rhodium atom or a ruthenium atom can be similarlyexemplified in the above-mentioned nickel compounds.

Among the metal compounds(II) represented by the general formula [11],specific examples of a compound in which a transition metal atom is aniron atom include 2,6-bis-[1-(2,6-dimethylphenylimino)ethyl]pyridineirondichloride, 2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl] pyridineirondichloride, 2,6-bis-[1-(2-tert-butylphenylimino)ethyl]pyridineirondichloride, [hydrotris(3,5-dimethylpyrazolyl)borate]iron chloride,[hydrotris(3,5-dimethylpyrazolyl) borate]iron bromide,[hydrotris(3,5-dimethylpyrazolyl)borate]iron iodide,[hydrotris(3,5-dimethylpyrazolyl)borate]iron methyl,[hydrotris(3,5-dimethylpyrazolyl)borate]iron ethyl,[hydrotris(3,5-dimethylpyrazolyl)borate]iron allyl,[hydrotris(3,5-dimethylpyrazolyl)borate]iron methallyl,[hydrotris(3,5-diethylpyrazolyl) borate]iron chloride,[hydrotris(3,5-diethylpyrazolyl)borate]iron bromide,[hydrotris(3,5-diethylpyrazolyl)borate]iron iodide,[hydrotris(3,5-diethylpyrazolyl)borate]iron methyl,[hydrotris(3,5-diethylpyrazolyl)borate]iron ethyl,[hydrotris(3,5-diethylpyrazolyl)borate]iron allyl,[hydrotris(3,5-diethylpyrazolyl)borate]iron methallyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron chloride,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron bromide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron iodide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron methyl,[hydrotris(3,5—di-tert-butylpyrazolyl)borate]iron ethyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron allyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron methallyl, and thelike.

Further, compounds wherein an iron atom is replaced with a cobalt atomor a nickel atom can be similarly exemplified in the above-mentionediron compounds.

Moreover, among the metal compounds(II) represented by the generalformula [11], specific examples of μ-oxo type compounds includeμ-oxobis{isopropylidene(cyclopentadienyl)(2-phenoxy)titanium chloride},μ-oxobis{isopropylidene(cyclopentadienyl)(2-phenoxy)titanium methoxide},μ-oxobis{isopropylidene(cyclopentadienyl)(3-tert--butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide},μ-oxobis{isopropylidene(methylcyclopentadienyl)(2-phenoxy)titaniumchloride},μ-oxobis{isopropylidene(methylcyclopentadienyl)(2-phenoxy)titaniummethoxide},μ-oxobis{isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide}, μ-oxobis{isopropylidene(tetramethylcyclopentadienyl)(2-phenoxy)titanium chloride},μ-oxobis{isopropylidene(tetramethylcyclopentadienyl)(2-phenoxy)titaniummethoxide},μ-oxobis{isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride}, μ-oxobis{isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide},μoxobis{dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium chloride},μoxobis{dimethylsilylene(cyclopentadienyl)(2-phenoxy)titaniummethoxide},μ-oxobis{dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride}, μ-oxobis{dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium methoxide},μ-oxobis{dimethylsilylene(methylcyclopentadienyl) (2-phenoxy)titaniumchloride},μ-oxobis{dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titaniummethoxide},μ-oxobis{dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide}, μ-oxobis{dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titanium chloride},μ-oxobis{dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titanium methoxide},μ-oxobis{dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium chloride},μ-oxobis{dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide}di-μ-oxobis[isopropylidene(cyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis[isopropylidene(methylcyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis[isopropylidene(tetramethylcyclopentadienyl)(2-phenoxy)titanium), di-μ-oxobisisopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis [dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis{dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titanium),di-μ-oxobis}dimethylsilylene(methylcyclopentadienyl)[(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-9-oxobis[dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium] and the like.

Furthermore, compounds in which a titanium atom is replaced with azirconium atom or a hafnium atom can be similarly exemplified in theabove-mentioned titanium compounds.

Specific Examples of the metal compounds(II) other than the metalcompounds represented by the general formula [11] and μ-oxo type metalcompounds include nickel chloride, nickel bromide, nickel iodide, nickelsulfate as a compound in which metal atom is nickel atom,nickel-nitrate, nickel perchlorate, nickel acetate, nickeltrifluoroacetate, nickel cyanide, nickel oxalate, nickelacetylacetonate, bis (allyl) nickel, bis(1,5-cyclooctadiene)nickel,dichloro(1,5-cyclooctadiene) nickel, dichlorobis(acetonitrile)nickel,dichlorobis(benzonitrile)nickel, carbonyltris(triphenylphosphine)nickel, dichlorobis(triethylphosphine)nickel,di-acetobis (triphenylphosphine)nickel,tetrakis(triphenylphosphine)nickel, dichloro[1,2-bis(diphenylphosphino)ethane]nickel,bis[1,2-bis(diphenylphosphino)ethane]nickel,dichloro[1,3-bis(diphenylphosphino)propane]nickel,bis[1,3-bis(diphenylphosphino)propane]nickel, tetraamine nickel nitrate,tetrakis(acetonitrile)nickel tetrafluoroborate, nickel phthalocyanine,etc.

Among the metal compounds(II), specific examples of a compound in whicha transition metal atom is a vanadium atom include vanadiumacetylacetonate, vanadium tetrachloride, vanadium oxy trichloride andthe like.

Among the metal compounds(II), specific examples of a compound in whicha transition metal atom is a samarium atom includebis(pentamethylcyclopentadienyl)samarium methyltetrahydrofuran and thelike.

Among the metal compounds(II), specific examples of a compound in whicha transition metal atom is an ytterbium atom includebis(pentamethylcyclopentadienyl)ytterbium methyltetrahydrofuran and thelike.

(wherein respective R^(g) groups independently represent a hydrogenatom, halogen atom or hydrocarbon group, they may be the same ordifferent, and two or more of them may be bonded mutually and may form aring. Xb groups independently represent a hydrogen atom, halogen atom orhydrocarbon group, they may be the same or different, and may be bondedmutually and may form a ring.)

These metal compounds(II) may be used alone, or in combination of 2 ormore kinds of the compounds.

In the metal compounds described above, as a metal compound(II) used inthe present invention, compounds represented by the general formula [11]are preferable.

Among these, metal compounds in which M in the general formula [10] is atransition metal are preferable, and further, particularly metalcompounds in which L in the general formula [10] is a group having atleast one cyclopentadiene type anion skeleton, are preferable.

(III) Organoaluminum Compound

As the organoaluminum compound (III) which is a component used for thecatalyst for addition polymerization of the present invention, knownorganoaluminum compounds can be used. The organoaluminum compoundindicated by the general formula [13] described below is preferable.

R^(h) _(b)AlZ_(3-b)  [13]

(wherein Rh represents a hydrocarbon group, all of Rhis may be the sameor different. Z represents a hydrogen atom, a halogen atom, an alkoxygroup, an aralkyloxy group or an aryloxy group, and “b” represents anumeral satisfying 0<b≦3.)

R^(h) in the general formula [13] representing the organoaluminumcompound is preferably a hydrocarbon group having 1 to 24 carbon atoms,and more preferably an alkyl group having 1 to 24 carbon atoms. Specificexamples include a methyl group, an ethyl group, a n-propyl group, an-butyl group, an isobutyl group, a n-hexyl group, a 2-methylhexylgroup, a n-octyl group and the like, and an ethyl group, a n-butylgroup, an isobutyl group or a n-hexyl group is preferable.

Further, specific example of a case in which Z is a halogen atomincludes a fluorine atom, a chlorine atom, a bromine atom, an iodineatom, and a chlorine atom is preferable.

The alkoxy group in Z is preferably an alkoxy group having 1 to 24carbon atoms, and specific examples include a methoxy group, an ethoxygroup, a n-propoxy group, an isopropoxy group, a n-butoxy group, asec-butoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxygroup, a n-hexoxy group, a n-octoxy group, a n-dodecoxy group, an-pentadecoxy group, a n-icosoxy -group and the like, and a methoxygroup, an ethoxy group or a tert-butoxy group is preferable.

Any one of these alkoxy groups may be substituted with a halogen atomsuch as a fluorine atom, a chlorine atom, a bromine atom or an iodineatom, an alkoxy group such as a methoxy group, an ethoxy group or thelike, or an aryloxy group such as a phenoxy group or the like.

The aryloxy group in Y is preferably an aryloxy group having 6 to 24carbon atoms, and specific examples include a phenoxy group, a2-methylphenoxy group, a 3-methyl phenoxy group, a 4-methylphenoxygroup, a 2,3-dimethyl phenoxy group, a 2,4-dimethylphenoxy group, a2,5-dimethylphenoxy group, a 2,6-dimethylphenoxy group, a3,4-dimethylphenoxy group, a 3,5-dimethylphenoxy group, a2,3,4-trimethylphenoxy group, a 2,3,5-trimethylphenoxy group, a2,3,6-trimethylphenoxy group, a 2,4,5-trimethylphenoxy group, a2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a2,3,4,5-tetramethylphenoxy group, a 2,3,4,6-tetramethylphenoxy group,2,3,5,6-tetramethylphenoxy group, a pentamethylphenoxy group, anethylphenoxy group, a n-propylphenoxy group, an isopropylphenoxy group,a n-butylphenoxy group, a sec-butylphenoxy group, a tert-butylphenoxygroup, a n-hexylphenoxy group, a n-octylphenoxy group, a n-decylphenoxygroup, a n-tetradecylphenoxy group, a naphthoxy group, an anthrathenoxygroup and the like.

Any one of these aryloxy groups may be substituted with a halogen atomsuch as a fluorine atom, a chlorine atom, a bromine atom, an iodine atomor the like, an alkoxy group such as a methoxy group, an ethoxy group orthe like, or an aryloxy group such as a phenoxy group or the like.

The aralkyloxy group in Y is preferably an aralkyloxy group having 7 to24 carbon atoms, and specific examples include a benzyloxy group, a(2-methylphenyl)methoxy group, a (3-methylphenyl)methoxy group, a(4-methylphenyl)methoxy group, a (2,3-dimethylphenyl)methoxy group, a(2,4-dimethylphenyl)methoxy group, a (2,5-dimethylphenyl)methoxy group,a (2,6-dimethylphenyl)methoxy group, a (3,4-dimethylphenyl)methoxygroup, a (3,5-dimethylphenyl)methoxy group, a(2,3,4-trimethylphenyl)methoxy group, a (2,3,5-trimethylphenyl)methoxygroup, a (2,3,6-trimethylphenyl)methoxy group, a(2,4,5-trimethylphenyl)methoxy group, a (2,4,6-trimethylphenyl)methoxygroup, a (3,4,5-trimethylphenyl)methoxy group, a(2,3,4,5-tetramethylphenyl)methoxy group, a(2,3,4,6-tetramethylphenyl)methoxy group, a(2,3,5,6-tetramethylphenyl)methoxy group, a (pentamethylphenyl)methoxygroup, an (ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group,an (isopropylphenyl)methoxy group, a (n-butylphenyl)methoxy group, a(sec-butylphenyl)methoxy group, a (tert-butylphenyl)methoxy group, a(n-hexylphenyl)methoxy group, a (n-octylphenyl)methoxy group, a(n-decylphenyl)methoxy group, a (n-tetradecylphenyl)methoxy group, anaphthylmethoxy group, an anthrathenylmethoxy group and the like, and abenzyloxy group is preferable.

Any one of these aralkyloxy groups may be substituted with a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom, an iodineatom or the like, an alkoxy group such as a methoxy group, an ethoxygroup or the like, or an aryloxy group such as a phenoxy group or thelike.

Specific examples of the organoaluminum compound represented by thegeneral formula (13) include trialkylaluminums such astrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like; dialkylaluminum chlorides such asdimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminumchloride, di-n-butylaluminum chloride, diisobutylaluminum chloride,di-n-hexylaluminum chloride and the like; alkylaluminum dichlorides suchas methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminumdichloride, n-butylaluminum dichloride, isobutylaluminum dichloride,n-hexylaluminum dichloride and the like; dialkylaluminum hydrides suchas dimethylaluminum hydride, diethylaluminum hydride,di-n-propylaluminum hydride, di-n-butylaluminum hydride,diisobutylaluminum hydride, di-n-hexylaluminum hydride and the like,alkyl(dialkoxy)aluminums such as methyl(dimethoxy)aluminum,methyl(diethoxy)aluminum, methyl(di-tert-butoxy)aluminum and the like;dialkyl(alkoxy)aluminums such as dimethyl(methoxy) aluminum,dimethyl(ethoxy) aluminum, dimethyl(tert-butoxy)aluminum and the like;alkyl(diaryloxy)aluminums such as methyl(diphenoxy)aluminum,methylbis(2,6-diisopropylphenoxy)aluminum,methylbis(2,6-diphenylphenoxy)aluminum and the like;dialkyl(aryloxy)aluminums such as dimethyl(phenoxy)aluminum,dimethyl(2,6-diisopropylphenoxy)aluminum,dimethyl(2,6-diphenylphenoxy)aluminum and the like, etc.

Among these, a trialkylaluminum is preferable, and trimethylaluminum,triethylaluminum, tri-n-butylaluminum, triisobutylaluminum ortri-n-hexylaluminum, is more preferable, and in particular,triisobutylaluminum or tri-n-hexylaluminum is preferable.

These organoaluminum compounds may be used alone, or in combination oftwo or more.

The ratio (molar ratio) of the amount used of the respective catalystcomponents in the present invention is not particularly limited, and themolar ratio of the component (I) to the component (II) is usually amolar ratio of a range of (I) (II)=from 1:1 to 10000:1, preferably from1:1 to 5000:1, and more preferably a molar ratio of a range of from 1:1to 1000:1. The amount used in case of using the component(III) isusually a molar ratio of a range of (II) (III)=from 0.1:1 to 1:10000,and preferably a molar ratio of a range of from 1:1 to 1:1000.

As the catalyst for addition polymerization of the present invention, areaction product obtained by preliminarily contacting the component (I)and the component (II), optionally, further the component (III) may bealso used, and they may be also used by being separately charged in apolymerization vessel. The arbitrary two components among them may bealso previously contacted, and further, another component may be alsocontacted.

When the respective components are used as a solution, the concentrationof the component (I) and the component (III) are usually 0.0001 to 100mmol/L converted to metal atom, and preferably 0.01 to 10 mmol/L,respectively. The concentration of the component (II) is usually 0.0001to 100 mmol/L converted to metal atom, and preferably 0.01 to 10 mmol/L.

The method of feeding the respective components in a reactor is notparticularly limited. A method of feeding the respective components in asolid condition, a method of feeding them in a condition of a solutionin which they are dissolved in a hydrocarbon solvent from whichcomponents such as moisture, oxygen and the like deactivating catalystcomponents are removed, or a suspension or a slurry, and the like arementioned.

Concerning the polymerization method, it should not be specificallylimited. For example, there are mentioned a solvent polymerization or aslurry polymerization in which an aliphatic hydrocarbon such as butane,pentane, hexane, heptane, octane or the like; an aromatic hydrocarbonsuch as benzene, toluene or the like; or a halogenated hydrocarbon suchas methylene dichloride or the like is used as a solvent, a bulkpolymerization in which polymerization is carried out in a liquidmonomer, a gas phase polymerization in which polymerization is carriedout in a gaseous monomer, a high-pressure polymerization method in whichpolymerization is carried out in a supercritical liquid condition at ahigh temperature under a high pressure, etc. As polymerization form,either of a batch-wise type and a continuous type are possible.

The polymerization temperature is usually from −100° C. to 350° C.,preferably from −20° C. to 30° C., and more preferably from 20° C. to300° C. The polymerization pressure is usually from 1 to 3500 kg/cm²G,preferably from 1 to 3000 kg/cm²G, and more preferably from 1 to 2000kg/cm²G. In general, the polymerization time is appropriately determinedaccording to the kind of a desired polymer and a reaction apparatus, anda range of form 1 minute to 20 hours can be adopted.

As monomers which can be used, any one of olefins having 2 to 100 carbonatoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons andpolar monomers can be used, and two or more monomers thereof can also beused, simultaneously. Specific examples thereof include olefins such asethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene-1,2-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, vinylcyclohexene and the like; diolefins such as1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene,5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene,5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene,5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene,1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene,1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene,1,3-cyclooctadiene, 1,3-cyclohexadiene and the like; cyclic olefins suchas norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene,5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene,tricyclodecene, tricycloundecene, pentacyclopentadecene,pentacyclohexadecene, 8-methyltetracyclododecene,8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene,5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene,5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene,8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene,8-cyanotetracyclododecene and the like; alkenylbenzenes such as styrene,2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene and the like;alkylstyrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene,p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene,2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene,3-methyl-5-ethylstyrene, p-tert-butylstyrene, p-sec-butylstyrene and thelike; bis(alkenyl)benzenes such as divinylbenzene and the like; alkenylaromatic hydrocarbons such as alkenylnaphthalenes and the like such as1-vinylnaphthalene and the like; polar monomers such as α,β-unsaturatedcarboxylic acids such as acrylic acid, methacrylic acid, fumaric acid,maleic anhydride, itaconic acid, itaconic anhydride,bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid and the like, and metalsalts thereof such as sodium, potassium, lithium, zinc, magnesium,calcium and the like; α,β-unsaturated carboxylic acid esters such asmethyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate,tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethylmethacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butylmethacrylate, isobutyl methacrylate and the like; unsaturateddicarboxylic acids such as maleic acid, itaconic acid and the like;vinyl esters such as vinyl acetate, vinyl propionate, vinyl capronate,vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate andthe like; unsaturated carboxylic acid glycidylate such as acrylic acidglycidylate, methacrylic acid glycidylate, itaconic acid monoglycidylateand the like; etc.

The present invention can be applied to homopolymerzation orcopolymerzation of these monomers. Specific examples of the monomerconstituting the copolymer include ethylene and propylene, ethylene and1-butene, ethylene and 1-hexene, propylene and 1-butene, and the like,but the present invention should not be limited thereto.

In order to control the molecular weight of a polymer, a chain transferagent such as hydrogen or the like can be added.

The catalyst for addition polymerization of the present invention isparticularly suitable as a catalyst for olefin polymerization, andsuitably used for a production process of an olefin polymer. The olefinpolymer is preferably a copolymer of ethylene with an t-olefin inparticular, and specifically, a linear low density polyethylene (LLDPE)is preferable. Further, a propylene polymer is preferably as the olefinpolymer in particular

EXAMPLE

The present invention is further illustrated in detail according toExamples and Comparative Examples below, but the present invention isnot limited thereto.

The measurement values of respective items in Examples were measuredaccording to methods described below.

(1) The content of α-olefin unit in a copolymer was determined by usinga calibration curve from the characteristic absorption of ethylene andα-olefin using an infrared spectrometer (FT-IR7300, manufactured byNIPPON BUNKO Inc.) and was represented as a short-chain branch (SCB)number per 1000 carbon atoms.

(2) Intrinsic viscosity ([η]):

It was measured at 135° C. in a tetralin solution using an Ubbelohdeviscometer.

(3) Measurement of ¹³C-NMR

JNM-EX270 (67.5 MHz, ¹³C) of Nihon Denshi Company was used for measuring¹³C-NMR. A deuterated solvent described in Example was used andmeasurement was carried out at room temperature.

(4) Molecular weight and molecular weight distribution:

They were determined under the under-mentioned conditions according to agel permeation chromatography (GPC). Calibration curve was preparedusing a standard polystyrene. Molecular weight distribution wasevaluated by a ratio (Mw/Mn) of weight average molecular weight (Mw) tonumber average molecular weight (Mn).

Equipment: 150° C. type, manufactured by Milipore Waters Co., Ltd.

Column: TSK-GEL GMH-HT; 7.5×600×2 columns

Measurement temperature: 140° C.

Solvent: O-dichlorobenzene

Measurement concentration: 5 mg/5 ml

(5) Melting point of a copolymer was determined using SSC-5200 of SeikoCo., Ltd. according to the condition below.

Raise of temperature: 40° C. to 150° C.(10° C./min.),

retaining for 5 minutes.

Cooling: 150° C. to 40° C.(5° C./min.),

retaining for 10 minutes.

Measurement: 40° C. to 160° C.(5° C./min.)

Example 1

(1) Synthesis of compound (I-1)

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon, 10 ml (10 mmol) of ZnEt₂(diethylzinc) (1.02M, hexanesolution) and 50 ml of toluene were charged and the mixture was cooledto −78° C. Thereto, 5.7 ml (10 mmol) of pentafluorophenol (1.78M, hexanesolution) was added dropwise. After completion of dropwise addition,temperature was gradually raised to room temperature, and stirring wasfurther carried out for 2 hours. Then, 89.0 mg (4.94 mmol) of H₂O wasgradually added dropwise by a micro syringe at room temperature. Thecontent became muddy in white. After completion of dropwise addition,stirring was further carried out for 11 hours. The white gel solidprepared was dried at room temperature under reduced pressure to obtain2.56 g of a white powder. As a result of measurements of ¹H-NMR and¹³C-NMR, a spectrum according to an unreacted Zn-Et structure wasconfirmed.

¹H-NMR (THF-d8): δ 1.18 (t,3H, J=7.9 Hz, ZnCH₂CH₃), 0.28 (q,2H, J=7.9Hz, ZnCH₂CH₃)

¹³C-NMR(THF-d8): δ 141.9 (m), 141.4 (m, JC-F=233 Hz), 139.0 (m, JC-F=245Hz), 131.7 (m, JC-F=236 Hz), 12.5 (s, ZnCH₂CH₃), −3.0 (s, ZnCH₂CH₃)

(2) Polymerization

After drying under vacuum an autoclave reactor having an inner volume of400 ml equipped with a stirrer and replacing the atmosphere thereof withargon, 190 ml of hexane as a solvent and 10 ml of 1-hexene as acomonomer were charged and the reactor was heated to 70° C. After theraise of temperature, ethylene was fed while adjusting at an ethylenepressure of 6 kg/cm². After the system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0 μmol of ethylenebis(indenyl) zirconium dichloride was charged, 22.1 mg (86.2 μmol-Zn) ofthe component (I-1) obtained in the above-mentioned (1) was furthercharged, and polymerization was started. The polymerization was carriedout for 30 minutes. As a result of the polymerization, 7.88 g of anethylene-1-hexene copolymer was obtained. Polymerization activity was1.6×10⁷ g/mol/h. SCB=13.73, [η]=1.24 dl/g, Mw=79000, Mw/Mn=1.7.

Example 2

(1) Synthesis of compound (I-2)

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon, 10 ml (10 mmol) of ZnEt₂ (1.02M, hexane solution) and 50 mlof toluene were charged and the mixture was cooled to −78° C. Thereto,6.9 ml (10 mmol) of pentafluorophenol (1.48M, hexane solution) was addeddropwise. After completion of dropwise addition, temperature wasgradually raised to room temperature, and stirring was further carriedout over night. Then, stirring was carried out for one hour under refluxcondition, and the mixture was cooled to room temperature. Then, 93.8 mg(5.21 mmol) of H₂O was gradually added dropwise by a micro syringe. Thecontent became white slurry-like. After completion of dropwise addition,stirring was carried out for 6 hours under reflux condition. Volatilematerials were removed by distillation under reduced pressure from thewhite slurry product prepared, and the solid prepared was dried at roomtemperature under reduced pressure to obtain 2.21 g of a white powder.

(2) Polymerization

After drying under vacuum an autoclave reactor having an inner volume of400 ml equipped with a stirrer and replacing the atmosphere thereof withargon, 190 ml of hexane as a solvent and 10 ml of 1-hexene as acomonomer were charged and the reactor was heated to 70° C. After theraise of temperature, ethylene was fed while adjusting at an ethylenepressure of 6 kg/cm². After the system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, and successively, 1.0 μmol ofethylenebis(indenyl)zirconium dichloride was charged, 23.4 mg (91.2μmol-Zn) of the compound (I-2) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 8.69 g ofan ethylene-1-hexene copolymer was obtained. Polymerization activity was1.7×10⁷ g/mol/h. SCB=16.46, [θ]=1.33 dl/g, Mw=77000, Mw/Mn=2.0.

Example 3

(1) Synthesis of compound (I-3)

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon after reduced pressure drying under vacuum, 10 ml (10 mmol)of a hexane solution of diethylzinc [1.02 mol/L (M)] and 50 ml oftetrahydrofuran were charged, and the mixture was cooled to −78° C. andstirred. Thereto, 6.9 ml (10 mmol) of pentafluorophenol (1.48M, hexanesolution) was added dropwise. After completion of dropwise addition thetemperature was gradually raised to room temperature, and stirring wascarried out for 2 hours. Then, 93.7 mg (5.20 mmol) of H₂O was graduallyadded dropwise by a micro syringe. The content became a yellowtransparent solution. After completion of dropwise addition, stirringwas carried out for 20 hours. Volatile materials were removed bydistillation under reduced pressure, and the solid prepared was dried at120° C. for 8 hours under reduced pressure to obtain 2.34 g of an ivorypowder. As a result of measurements of ¹H-NMR and ¹³C-NMR, a spectrumderived from a Zn-Et structure could not be confirmed.

¹³C-NMR(THF-d8): δ 141.9(m), 141.4 (m, JC-F=234 Hz), 139.0 (m, JC-F=249Hz), 131.6 (m, JC-F=236 Hz)

(2) Polymerization

After drying under vacuum an autoclave reactor having an inner volume of400 ml equipped with a stirrer and replacing the atmosphere thereof withargon, 190 ml of hexane as a solvent and 10 ml of 1-hexene as acomonomer were charged and the reactor was heated to 70° C. After theraise of temperature, ethylene was fed while adjusting at an ethylenepressure of 6 kg/cm². After the system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0 μmol ofethylenebis(indenyl)zirconium dichloride was charged, 31.4 mg (122μmol-Zn) of the compound (I-3) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 15.75 gof an ethylene-1-hexene copolymer was obtained. Polymerization activitywas 3.2×10⁷ g/mol/h. SCB=15.23, [η]=1.24 dl/g, Mw=72000, Mw/Mn=2.0.

Example 4

(1) Synthesis of compound (I-4)

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon after reduced pressure drying under vacuum, 20 ml (20 mmol)of a hexane solution of diethylzinc (1.02M) and 100 ml oftetrahydrofuran were charged, and the mixture was cooled to −78° C. andstirred. Thereto, 4.4 ml (5.1 mmol) of pentafluorophenol (1.17M, hexanesolution) was added dropwise. After completion of dropwise addition, thetemperature was gradually raised to room temperature, and stirring wascarried out for 2 hours. Then, 321 μl (17.8 mmol) of H₂O was graduallyadded dropwise by a micro syringe. After completion of dropwiseaddition, stirring was carried out for 14 hours. Volatile materials wereremoved by distillation under reduced pressure, and the solid preparedwas dried at 120° C. for 8 hours under reduced pressure to obtain anivory powder.

(2) Polymerization

After drying under vacuum an autoclave reactor having an inner volume of400 ml equipped with a stirrer and replacing the atmosphere thereof withargon, 190 ml of hexane as a solvent and 10 ml of 1-hexene as acomonomer were charged and the reactor was heated to 70° C. After theraise of temperature, ethylene was fed while adjusting at an ethylenepressure of 6 kg/cm². After the inside of system was stabilized, 0.25mmol of triisobutylaluminum was charged, successively, 0.3 μmol ofethylenebis(indenyl)zirconium dichloride was charged, 9.0 mg (72μmol-Zn) of the compound (I-4) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 2.4 g ofan ethylene-hexene-1 copolymer was obtained Polymerization activity was1.6×10⁷ g/mol/h. SCB=15.54.

Example 5

(1) Synthesis of compound (I-5)

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon after reduced pressure drying under vacuum, 20 ml (20 mmol)of a hexane solution of diethylzinc (1.02 M) and 10 ml oftetrahydrofuran were charged, and the mixture was cooled to −78° C. andstirred. Thereto, 8.7 ml (10 mmol) of pentafluorophenol (1.17M, hexanesolution) was added dropwise. After completion of dropwise addition, thetemperature was gradually raised to room temperature, and stirring wascarried out for 2 hours. Then, 275 μl (15.3 mmol) of H₂O was graduallyadded dropwise by a micro syringe. After completion of dropwiseaddition, stirring was carried out at room temperature over night.Volatile materials were removed by distillation under reduced pressure,and the solid prepared was dried at 12° C. for 8 hours under reducedpressure to obtain an ivory powder.

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 0.3 μmol ofethylenebis(indenyl)zirconium dichloride was charged, 9.3 mg (55μmol-Zn) of the compound (I-5) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 11.06 gof an ethylene-1-hexene copolymer was obtained. Polymerization activitywas 7.4×10⁷ g/mol/h. SCB=12.79.

Example 6

(1) Polymerization

After drying under vacuum an autoclave reactor having an inner volume of400 ml equipped with a stirrer and replacing the atmosphere thereof withargon, 190 ml of hexane as a solvent and 10 ml of 1-hexene as acomonomer were charged and the reactor was heated to 70° C. After theraise of temperature, ethylene was fed while adjusting at an ethylenepressure of 6 kg/cm². After the system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 0.3 μmol ofethylenebis(indenyl) zirconium dichloride was charged, 23.2 mg (90.5μmol-Zn) of the compound (I-3) obtained in Example 3(1) was furthercharged, and polymerization was started. The polymerization was carriedout for 30 minutes. As a result of the polymerization, 6.9 g of anethylene-1-hexene copolymer was obtained. Polymerization activity was4.6×10⁷ g/mol/h. SCB=15.39.

Example 7

(1) Synthesis of compound (I-6)

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon after reduced pressure drying under vacuum, 20 ml (20 mmol)of a hexane solution of diethylzinc (1.02M) and 100 ml oftetrahydrofuran were charged, and the mixture was cooled to −78° C. andstirred. Thereto, 26.2 ml (30.7 mmol) of pentafluorophenol (1.17M,hexane solution) was added dropwise. After completion of dropwiseaddition, the temperature was gradually raised to room temperature, andstirring was carried out for 2 hours. Then, 92 μl (5.1 mmol) of H₂O wasgradually added dropwise by a micro syringe. After completion ofdropwise addition, stirring was carried out at room temperature overnight. Volatile materials were removed by distillation under reducedpressure, and the solid prepared was dried at 120° C. for 8 hours underreduced pressure to obtain an ivory powder.

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 0.39 mol ofethylenebis(indenyl)zirconium dichloride was charged, 27.0 mg (78.5μmol-Zn) of the compound (I-6) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 1.3 g ofan ethylene-hexene-1 copolymer was obtained. Polymerization activity was8.7×10⁶ g/mol/h. SCB=17.04.

Example 8

(1) Polymerization of propylene

A magnetic stirrer was placed in an autoclave having an inner volume of100 ml, it was dried under vacuum, and the atmosphere was replaced withargon. Thereto, 70.6 mg (275 μmol-Zn) of the compound (I-2) obtained inExample 2(1), 0.5 mmol of triisobutylaluminum and 2 μmol ofethylenebis(indenyl)zirconium dichloride were charged. In the autoclave,40 g of propylene was charged, temperature was raised to 40° C., andpolymerization was started. The polymerization was carried out for 60minutes. As a result of the polymerization, 2.23 g of a propylenepolymer was obtained. Polymerization activity was 2.2×10⁶ g/mol/h.Mw=21000, Mw/Mn=1.9.

Example 9

(1) Synthesis of Compound (I-7)

Into a 300 ml four-necked flask in which the atmosphere was replacedwith argon after reduced pressure drying under vacuum, 16.49 g (90.07mmol) of pentafluoroaniline and 70 ml of toluene were charged, and themixture was cooled to 0° C. and stirred. Thereto, 176.6 ml ofdiethylzinc (1.02M, hexane solution) was added, then the temperature wasgradually raised to room temperature, and stirring was carried out overnight. The content article became a white slurry. After stirring wascarried out for 8 hours under reflux condition, volatile materials wereremoved by distillation under reduced pressure to obtain 18.32 g of asolid product.

After drying the solid product under reduced pressure in vacuum, 3.68 gof the solid product and 100 ml of toluene were charged in the 300 mlfour-necked flask in which the atmosphere was replaced with argon, andthe mixture was stirred at room temperature. Thereto, 17.0 ml (19.9mmol) of pentafluorophenol (1.17M, hexane solution) was added, andstirring was carried out for 68 hours. Volatile materials were removedby distillation under reduced pressure to obtain a white solid.

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1 μmol ofethylenebis(indenyl)zirconium dichloride was charged, 40.8 mg (120μmol-Zn) of the compound (I-7) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 1.02 g ofan ethylene-1-hexene copolymer was obtained. Polymerization activity was2.0×10⁶ g/mol/h.

Example 10

Into a 300 ml four-necked flask in which the atmosphere was replacedwith argon, 106 ml of tetrahydrofuran and 40 ml (80 mmol) of ZnEt₂ (2M,hexane solution) were charged, and the mixture was cooled to 4° C.Thereto, 14.5 ml (32 mmol) of pentafluorophenol (2.21M, tetrahydrofuransolution) was added dropwise for 50 minutes. After completion ofdropwise addition, stirring was further carried out at 50° C. for 1hour. The temperature was lowered to 20° C. by ice bath, and 7.3 ml(72.3 mmol) of H₂O (9.9M, tetrahydrofuran solution) was added dropwisefor 1 hour. After completion of dropwise addition, stirring was furthercarried out for 2 hours, then the mixture was stood alone at roomtemperature over night. Then, stirring was carried out for 8 hours underreflux condition (63° C.). As a result, the component (A) was obtainedas an yellow transparent solution.

Example 11

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of ZnEt₂ (2M,hexane solution) were charged, and the mixture was cooled to 500.Thereto, 34.3 ml (80 mmol) of 3,4,5-trifluorophenol (2.33M,tetrahydrofuran solution) was added dropwise for 120 minutes. Aftercompletion of dropwise addition, stirring was carried out at 5° C. for90 minutes and then, further at 40° C. for 70 minutes. Then, thetemperature was lowered to 20° C. by ice bath, and 0.72 ml (40 mmol) ofH₂O was added dropwise for 80 minutes. After completion of dropwiseaddition, stirring was carried out at 200° C. for 60 minutes and then,further, at 40° C. for 120 minutes. As a result, the mixture wasseparated into a transparent liquid article and an yellow gel article.After standing them alone at room temperature over night, the volatilecomponents were removed by distillation, and drying was carried out at120° C. for 8 hours under reduced pressure. As a result, 17.05 g of anyellow solid product was obtained.

Example 12

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of ZnEt₂ (2M,hexane solution) were charged, and the mixture was cooled to 50° C.Thereto, 13.7 ml (32 mmol) of 3,4,5-trifluorophenol (2.33M,tetrahydrofuran solution) was added dropwise for 45 minutes. Aftercompletion of dropwise addition, stirring was carried out at 5° C. for90 minutes and then, further at 40° C. for 70 minutes. Then, thetemperature was lowered to 20° C. by ice bath, and 1.30 ml (72 mmol) ofH₂O was added dropwise for 145 minutes. After completion of dropwiseaddition, stirring was carried out at 20° C. for 60 minutes and then,further, at 40° C. for 120 minutes. As a result, the mixture wasseparated into a transparent liquid article and an yellow gel article.After standing them alone at room temperature over night, the volatilecomponents were removed by distillation, and drying was carried out at120° C. for 8 hours under reduced pressure. As a result, 10.39 g of anyellow solid product was obtained.

Example 13

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of ZnEt₂ (2M,hexane solution) were charged, and the mixture was cooled to 5° C.Thereto, 34.3 ml (80 mmol) of 3,5-difluorophenol (2.33M, tetrahydrofuransolution) was added dropwise for 120 minutes. After completion ofdropwise addition, stirring was carried out at 5° C. for 90 minutes andthen, further at 40° C. for 70 minutes. Then, the temperature waslowered to 20° C. by ice bath, and 0.72 ml (40 mmol) of H₂O was addeddropwise for 80 minutes. After completion of dropwise addition, stirringwas carried out at 20° C. for 60 minutes and then, further, at 40° C.for 120 minutes. As a result, a white yellow slurry article wasobtained. After standing it alone at room temperature over night, thevolatile components were removed by distillation, and drying was carriedout at 120° C. for 8 hours under reduced pressure. As a result, 14.66 gof an yellow solid product was obtained.

Example 14

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of ZnEt₂ (2M,hexane solution) were charged, and the mixture was cooled to 5° C.Thereto, 34.3 ml (80 mmol) of perfluoro-tert-butanol (2.33M,tetrahydrofuran solution) was added dropwise for 120 minutes. Aftercompletion of dropwise addition, stirring was carried out at 5° C. for90 minutes and then, further at 40° C. for 70 minutes. Then, thetemperature was lowered to 20° C. by ice bath, and 0.72 ml (40 mmol) ofH₂O was added dropwise for 80 minutes. After completion of dropwiseaddition, stirring was carried out at 20° C. for 60 minutes and then,further, at 40° C. for 120 minutes. As a result, a white yellow solutionwas obtained. After standing it alone at room temperature over night,the volatile components were removed by distillation, and drying wascarried out at 120° C. for 8 hours under reduced pressure. As a result,26.35 g of an yellow solid product was obtained.

Example 15

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of ZnEt₂ (2M,hexane solution) were charged, and the mixture was cooled to 5° C.Thereto, 34.3 ml (80 mmol) of 1,1,1,3,3,3-hexafluoro-2-propanol (2.33M,tetrahydrofuran solution) was added dropwise for 120 minutes. Aftercompletion of dropwise addition, stirring was carried out at 5° C. for90 minutes and then, further at 40° C. for 70 minutes. Then, thetemperature was lowered to 20° C. by ice bath, and 0.72 ml (40 mmol) ofH₂O was added dropwise for 80 minutes. After completion of dropwiseaddition, stirring was carried out at 20° C. for 60 minutes and then,further, at 40° C. for 120 minutes. As a result, a white yellow solutionwas obtained. After standing it alone at room temperature over night,the volatile components were removed by distillation, and drying wascarried out at 120° C. for 8 hours under reduced pressure. As a result,15.47 g of an yellow solid product was obtained.

Comparative Example 1

(1) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.01 mol ofethylenebis(indenyl)zirconium dichloride was charged, 0.1 ml (100 mol)of ZnEt₂ (1.02M, hexane solution) was further charged, andpolymerization was started. The polymerization was carried out for 30minutes. As a result of the polymerization, only a trace of a polymerwas obtained.

Example 16

(1) Synthesis of μ-oxo-bis(diethylzinc)

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon after reduced pressure drying under vacuum, 10 ml (10 mmol)of a hexane solution of diethylzinc (1.02 mol/L) and 50 ml of toluenewere charged and the mixture was stirred. Thereto, 89.2 mg (4.95 mmol)of H₂O was gradually added dropwise at room temperature.

The content article became opaque in yellow in accordance withproceeding of the reaction. After completion of dropwise addition,stirring was further carried out for 11 hours. The solvent was removedby distillation under reduced pressure, and drying was carried out toobtain 0.245 g of an yellow solid.

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0, mol ofethylenebis(indenyl)zirconium dichloride was charged, 29.9 mg (146 μmol)of 9-oxo-bis(diethylzinc) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 0.663 gof an ethylene-1-hexene copolymer was obtained. Polymerization activitywas 1.3×10⁶ g/mol/h. SCB=13.96, [θ]=1.30 dl/g, Mw=88000, Mw/Mn=1.9.

Example 17

(1) Synthesis of bis(pentafluorophenoxy)zinc

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon after reduced pressure drying under vacuum, 50 ml of hexaneand 10 ml (10 mmol) of a hexane solution of diethylzinc (1.00 mol/L)were charged and the mixture was cooled to −78° C. Thereto, 20 ml (20mmol) of a hexane solution (1.0 mol/L) of pentafluorophenol wasgradually added dropwise at room temperature. The content article becamewhite slurry in accordance with proceeding of the reaction. Aftercompletion of dropwise addition, the temperature was gradually raised toroom temperature, and stirring was further carried out for 4 hours. Thewhite solid prepared was separated by filtration with a glass filter,and drying was carried out under reduced pressure to obtain 3.41 g (7.90mmol, 79%) of bis(pentafluorophenoxy)zinc as a white solid.

¹³C-NMR (THF-d8): δ 141.4 (m, JC-F=233 Hz), 141.8 (m), 139.0 (m,JC-F=249 Hz), 131.7 (m, JC-F=236 Hz)

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0 μmol ofethylenebis(indenyl)zirconium dichloride was charged, 40 mg (92 μmol) ofthe zinc compound obtained in the above-mentioned (1) was furthercharged, and polymerization was started. The polymerization was carriedout for 30 minutes. As a result of the polymerization, 1.35 g of anethylene-1-hexene copolymer was obtained. Polymerization activity was2.7×10⁶ g/mol/h. SCB=16.8, [θ]=1.41 dl/g, Mw 97000, Mw/Mn=2.2. Meltingpoint was 111.5° C.

Example 18

(1) Synthesis of bis(pentafluorophenoxyzincoxy) methylborane compound

Into a 200 ml four-necked flask in which the atmosphere was replacedwith argon, 655.4 mg (10.6 mmol) of methylboric acid (97%) and 50 ml oftoluene were charged and the mixture was cooled to −78° C. Whilevigorously stirring the slurry article, 20.8 ml (21.2 mmol) of ZnEt₂(1.02M, hexane solution) was added dropwise. A white gel precipitate wasprepared in accordance with increase of the amount of dropwise addition.After completion of dropwise addition, the temperature was graduallyraised to room temperature, and stirring was further carried out for 2hours. Thereto, 11.9 ml (21.2 mmol) of pentafluorophenol (1.78M, hexanesolution) was gradually added dropwise, and stirring was further carriedout for 11 hours. The solvent was removed by distillation under reducedpressure, and drying was carried out to obtain 6.06 g of a white powder.

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0% mol ofethylenebis(indenyl)zirconium dichloride was charged, 34.2 mg (61.7μmol) of the zinc compound obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 3.42 g ofan ethylene-1-hexene copolymer was obtained. Polymerization activity was6.8×10⁶ g/mol/h.

Example 19

(1) Synthesis of compound (I-8)

Into a 100 ml flask in which the atmosphere was replaced with argon,18.3 ml (18.7 mmol) of diethylzinc (1.02M, hexane solution) and 10 ml oftoluene were charged and the mixture was cooled to −78° C. Thereto, 10.5ml (18.7 mmol) of pentafluorophenol (1.78M, hexane solution) wasgradually added dropwise. After completion of dropwise addition,temperature was gradually raised to room temperature, and stirring wasfurther carried out for 1 hour. Then, 10 ml of a toluene solution of1.01 g (9.36 mmol) of 1,3-cyclopentanediol (a mixture of cis-isomer andtrans-isomer; manufactured by Aldrich Co., Ltd.; purity=95%) wasgradually added dropwise at room temperature, and stirring was carriedout over night. Then, the solvent was removed by distillation underreduced pressure, and the solid prepared was dried at room temperatureunder reduced pressure to obtain 5.44 g of the compound (I-8).

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0 μmol ofethylenebis(indenyl)zirconium dichloride was charged, 36.3 mg (122μmol-Zn) of the compound (I-8) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 0.53 g ofan ethylene-1-hexene copolymer was obtained. Polymerization activity was1.1×10⁶ g/mol/h.

Example 20

(1) Synthesis of compound (I-9)

Into a 100 ml flask in which the atmosphere was replaced with argon,1.01 g (8.04 mmol) of 1,2,3-trihydroxybenzene and 30 ml of toluene werecharged, and the mixture was stirred and cooled to 0° C. Thereto, 15.8ml (16.1 mmol) of diethylzinc (1.02M, hexane solution) was addeddropwise. After completion of dropwise addition, temperature wasgradually raised to room temperature, and stirring was further carriedout for 24 hours. Thereto, 4.0 ml (8.0 mmol) of pentafluorophenol (2M,toluene solution) was added dropwise at room temperature. Aftercompletion of dropwise addition, and stirring was further carried outover night. Then, volatile materials were removed by distillation, andthe solid prepared was dried at room temperature under reduced pressureto obtain the compound (I-9).

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0 μmol ofethylenebis(indenyl)zirconium dichloride was charged, 26.0 mg (11μmol-Zn) of the compound (I-9) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 0.24 g ofan ethylene-1-hexene copolymer was obtained. Polymerization activity was4.8×10⁵ g/mol/h.

Example 21

(1) Synthesis of compound (I-10)

Into a 100 ml flask in which the atmosphere was replaced with argon,1.02 g (8.07 mmol) of 1,2,3-trihydroxybenzene and 30 ml of toluene werecharged, and the mixture was stirred and cooled to oOC. Thereto, 23.7 ml(24.2 mmol) of diethylzinc (1.02M, hexane solution) was added dropwise.After completion of dropwise addition, temperature was gradually raisedto room temperature, and stirring was further carried out for 24 hours.Thereto, 12.1 ml (24.2 mmol) of pentafluorophenol (2M, toluene solution)was added dropwise at room temperature. After completion of dropwiseaddition, and stirring was further carried out over night. Then,volatile materials were removed by distillation, and the solid preparedwas dried at room temperature under reduced pressure to obtain 7.89 g ofthe compound (I-10).

(2)Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0% mol ofethylenebis(indenyl)zirconium dichloride was charged, 38.6 mg (133μmol-Zn) of the compound (I-10) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 0.13 g ofan ethylene-1-hexene copolymer was obtained. Polymerization activity was2.6×10⁵ g/mol/h.

Example 22

(1) Synthesis of Compound (I-11)

Into a 100 ml flask in which the atmosphere was replaced with argon, 8.0ml (8.2 mmol) of diethylzinc (1.02M, hexane solution) and 10 ml oftoluene were charged, and the mixture was stirred and cooled to −78° C.Thereto, 4.6 ml (8.2 mmol) of pentafluorophenol (1.78M, toluenesolution) was gradually added dropwise. After completion of dropwiseaddition, temperature was gradually raised to room temperature, andstirring was further carried out for 1 hour. Then, 0.97 g (2.0 mmol) ofcalix[4]arene (89%) (manufactured by aldrich Co,) (2M, toluene solution)was added, and stirring was carried out over night. Then, volatilematerials were removed by distillation, and the solid prepared was driedat room temperature under reduced pressure to obtain 2.52 g of thecompound (I-11).

(2) Polymerization

After drying under vacuum an autoclave having an inner volume of 400 mlequipped with a stirrer and replacing the atmosphere thereof with argon,190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer werecharged and the reactor was heated to 70° C. After the raise oftemperature, ethylene was fed while adjusting at an ethylene pressure of6 kg/cm². After the inside of system was stabilized, 0.25 mmol oftriisobutylaluminum was charged, successively, 1.0/1 mol ofethylenebis(indenyl)zirconium dichloride was charged, 41.2 mg (117μmol-Zn) of the compound (I-11) obtained in the above-mentioned (1) wasfurther charged, and polymerization was started. The polymerization wascarried out for 30 minutes. As a result of the polymerization, 0.084 gof an ethylene-hexene-1 copolymer was obtained. Polymerization activitywas 1.7×10⁵ g/mol/h.

As described above in detail, according to the present invention, acompound other than a compound of Group XIII as a compound capable offorming a catalyst for addition polymerization which reveals a highpolymerization activity by using as a catalyst aid component foractivation, is provided, and a production method of the compound, acatalyst component for addition polymerization comprising the compound,a catalyst for addition polymerization which is made by using thecompound and reveals a high polymerization activity, and an efficientprocess for producing an olefin polymer using the catalyst for additionpolymerization, are provided.

What is claimed is:
 1. An electron withdrawing group-containing metalcompound (I) selected from the group consisting of [A] to [E] describedbelow: [A] A compound obtained by contacting (a), (b) and (c) describedbelow in the presence of an ether compound as a solvent: (a) a compoundrepresented by the general formula [1], M¹L¹C  [1] (b) a compoundrepresented by the general formula [2] R¹ _(p-1)T¹H  [2], and (c) acompound represented by the general formula [3] R² _(q-2)J¹H₂  [3] wherein in each of the general formulae [1] to [3], M¹ represents anatom of the Group III to the Group XII or lanthanide series of thePeriodic Table; c represents a valence of M¹; L¹ represents a hydrogenatom, a halogen atom or a hydrocarbon group; when a plural number ofL¹'s exist, they may be mutually the same or different; R¹ represents anelectron-withdrawing group or a group containing an electron-withdrawinggroup; R² represents a hydrocarbon group or a halogenated hydrocarbongroup; when a plural number of R²'s exist, they may be mutually the sameor different; each of T¹ and J¹ independently represents an atom ofGroup XV or Group XVI of the Periodic Table; and each of p and qrepresents a valence of T¹ and J¹, respectively; [B] A compound obtainedby contacting (d), (e) and (f) described below: (d) a compoundrepresented by the general formula [4] M²L²d  [4] (e) a compoundrepresented by the general formula [5] R³ _(r-1)T²H  [5] and (f) acompound represented by the general formula [6] R⁴(J²H_(e-1))_(f)  [6] wherein in each of the general formulae [4]to [6], M² represents anatom of Group III to Group XII or lanthanide series of the PeriodicTable; d represents a valence of M²; L² represents a hydrogen atom, ahalogen atom or a hydrocarbon group; when a plural number of L²'s exist,they may be mutually the same or different; R³ represents anelectron-withdrawing group or a group containing an electron-withdrawinggroup; R⁴ represents an organic group having a valence of f; each of T²and J² independently represents an atom of the Group XV or Group XVI ofthe Periodic Table; r represents a valence of T²; e represents a valenceof J²; and f is an integer of 2 to 10; [C] A compound represented by thegeneral formula [7]

 wherein M³ represents an atom of the Group III to Group XII orlanthanide series of the Periodic Table; when a plural number of M³'sexist, they may be mutually the same or different; T³ represents an atomof the Group XIV, Group XV or Group XVI of the Periodic Table; when aplural number of T³'s exist, they may be mutually the same or different;R⁵ represents an electron-withdrawing group or a group containing anelectron-withdrawing group; when a plural number of R⁵'s exist, they maybe mutually the same or different; R⁶ represents a hydrocarbon group; aplural number of R⁶'s may be mutually the same or different; grepresents a valence of M³; s represents a valence of T³; and hrepresents a numeral of 1 or more; [D] A compound represented by thegeneral formula [8], M⁴(X¹R⁷ _(i))_(t)R⁸ _(j-t)  [8]  wherein M⁴represents an atom of the Group III to Group XII or lanthanide series ofthe Periodic Table; X¹ represents an atom of the Group XIV, Group XV orGroup XVI of the Periodic Table; when a plural number of X¹'s exist,they may be mutually the same or different; R⁷ represents anelectron-withdrawing group or a group containing an electron-withdrawinggroup; when a plural number of R⁷'s exist, they may be mutually the sameor different; R⁸ represents a hydrogen atom, a halogen atom or ahydrocarbon group; a plural number of R⁸'s may be mutually the same ordifferent; j represents a valence of M⁴; t represents a numeralsatisfying 0<t≦j; and i represents a numeral less by one than thevalence of X¹; and [E] A compound represented by the general formula [9][(R⁹ _(u-1)X²)k⁻¹ M⁵O]_(m) T⁴R¹⁰ _(3-m)  [9]  wherein M⁵ represents anatom of the Group III to Group XII or lanthanide series of the PeriodicTable; when a plural number of M⁵'s exist, they may be mutually the sameor different; X² represents an atom of the Group XIV, Group XV or GroupXVI of the Periodic Table; when a plural number of X²'s exist, they maybe mutually the same or different; R⁹ represents an electron-withdrawinggroup or a group containing an electron-withdrawing group; when a pluralnumber of R⁹'s exist, they may be mutually the same or different; T⁴represents an atom of the Group XIII of the Periodic Table, R¹⁰represents a hydrogen atom, a halogen atom or a hydrocarbon group; whena plural number of R¹⁰'s exist, they may be mutually the same ordifferent; k represents a valence of M⁵; u represents a valence of X²;and m represents a numeral satisfying 1≦m≦3.
 2. The compound accordingto claim 1, wherein each of T¹, T², T³, X¹ and X² is independently anitrogen atom or an oxygen atom.
 3. The compound according to claim 1,wherein each of R¹, R³, R⁵, R⁷ and R⁹ is independently a halogenatedhydrocarbon group.
 4. The compound according to claim 2, wherein each ofR¹, R³, R⁵, R⁷ and R⁹ is independently a halogenated hydrocarbon group.5. The compound according to claim 1, wherein each of M¹, M², M³, M⁴ andM⁵ is independently an atom of the Group XII.
 6. The compound accordingto claim 1, wherein each of T¹, T², T³, X¹ and X² is independently anitrogen atom or an oxygen atom and each of M¹, M², M³, M⁴ and M⁵ isindependently an atom of the Group XII.
 7. The compound according toclaim 5, wherein said atom of the Group XII is zinc.
 8. The compoundaccording to claim 6, wherein said atom of the Group XII is zinc.
 9. Thecompound according to claim 1, wherein T⁴ in the general formula [9] isa boron atom.
 10. The compound according to claim 1, wherein X¹R⁷ _(i)is a fluoroalkyloxy group or a fluoroaryloxy group in the generalformula [8].
 11. The compound according to claim 1, wherein the compound[C] is a μ-oxo-bis(alkylzinc) or a μ-oxo-bis(arylzinc).